Aromatic polyester polyether polyols, polyurethanes made therefrom and building materials comprising same

ABSTRACT

This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present disclosure. The disclosure provides aromatic polyester polyether polyols and compositions comprising such polyols. The disclosed aromatic polyester polyether polyols and compositions including same are the products of the transesterification reaction of polyethylene terephthalate (“PET”) and an ethoxylated triol, namely glycerin or trimethylolpropane, wherein the degree of ethoxylation is from 1 to 9 moles. At least some of the PET used to generate the aromatic polyester polyether polyols is derived from recycled PET. The disclosed aromatic polyester polyether polyols have utility in preparing polyurethane materials, for example.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.62/573,842, filed Oct. 18, 2017, and U.S. Provisional Application No.62/722,874, filed Aug. 25, 2018. The disclosures of each of theseapplications are incorporated herein in their entireties.

FIELD OF THE DISCLOSURE

The disclosure relates to aromatic polyester polyether polyol materialsderived from the transesterification of polyethylene terephthalate witheither glycerin or trimethylolpropane, wherein each of these triols,independently, has a degree of ethoxylation of from 1 to 9. Thegenerated aromatic polyester polyether polyols exhibit beneficially lowviscosities. Such aromatic polyester polyol materials also impartimprovements to polyurethane materials generated therefrom, includingfire/heat resistance, adhesion, and impact resistance, among otherthings. The disclosure also relates to useful materials coated with suchimproved polyurethane materials, and substrates made from suchpolyurethanes. The polyurethane compositions can be foamed or unfoamed,and filled or unfilled. Yet further, the disclosure relates to processesof making the aromatic polyester polyether polyols, the polyurethanes,and useful materials incorporating such polyurethanes.

BACKGROUND OF THE DISCLOSURE

Polyethylene terephthalate, commonly abbreviated “PET,” consists ofpolymerized units of the monomer ethylene terephthalate, with repeating(C₁₀H₈O₄) units. PET is the most common thermoplastic polymer resin ofthe polyester family and is used in fibers for clothing and carpets,containers for liquids and foods, and as componentry, among otherthings. The majority of the world's PET production is for syntheticfibers (in excess of 60%), with bottle production accounting for about30% of global demand. Polyester makes up about 18% of global polymerproduction.

While PET is recyclable in many locations, typically PET waste has beenlandfilled due to the cost of recycling this material into usefulmaterials. It has not been cost effective to recycle PET into useablenew materials because it has been cheaper to generate materials frompetrochemical materials than from the depolymerization of waste PETwhich, when coupled with the general availability of landfill space, hasdisincentivized PET recycling. However, given the increasing cost andenvironmental impact of petroleum-derived polymers like PET, as well asthe decreasing availability of landfill space in many parts of theworld, recycling of PET is becoming more desirable. Thus, there is anincreasing focus on development of cost effective and value-addedmethods to recycle PET to generate new products.

Terminology for plastics recycling includes four categories:

-   -   Primary (mechanical reprocessing into a product with equivalent        properties) is often referred to as “closed-loop” recycling;    -   Secondary (mechanical reprocessing into products having reduced        property requirements than the previous polymer), referred to as        “downgrading;”    -   Tertiary is described as “chemical” or “feedstock” recycling and        applies when the polymer is de-polymerized to its chemical        constituents to be used to generate new polymers or other useful        chemicals; and    -   Quaternary is energy recovery, energy from waste, such as by        burning for fuel to utilize the petrochemical components        therein.

In general terms, tertiary recycling has the advantage of recovering thepetrochemical constituents of the polymer, which can then be used tore-manufacture the polymer or to make other chemicals. However, whiletechnically feasible, it has generally been found to be uneconomicwithout significant government or other subsidies because of the lowprice of petrochemical feedstock as compared to the plant and processcosts incurred to produce monomers from waste polymers. This is notsurprising because depolymerization effectively involves reversing theenergy-intensive polymerization previously carried out during firstorder PET manufacturing processes.

One of the useful materials that has been a goal of tertiary PETrecycling is the generation of aromatic polyester polyols as rawmaterials for polyurethane polymers, that is, to substitute for thepetrochemical feedstock that would otherwise be needed to obtain thesematerials. When the aromatic polyester polyether polyol is generatednatively—that is, not from the recycling of PET—the aromatic polyesterpolyol can be made by condensing aromatic diacids, diesters, oranhydrides (e.g., terephthalic acid, dimethyl terephthalate) withglycols such as ethylene glycol, propylene glycol, diethylene glycol, orthe like. When PET waste is depolymerized for generation of aromaticpolyester polyol via glycolysis, ethylene glycol, diethylene glycol,propylene glycol, or dipropylene glycol are typically used. Ethyleneglycol has been reported as the most reactive glycol for PET glycolysis.As would be appreciated, transesterification via glycolysis converts thepolymer to a mixture of glycols and low-molecular-weight PET oligomers,and the transesterification products can be modified for use with avariety of chemicals after completion of glycolysis to provide anaromatic polyester polyol that is workable in a polyurethane reaction.

Such aromatic polyester polyol products of the glycolysis of PET can beused in the preparation rigid polyurethane foams (“RPUF”). RPUFs can beused as insulating materials due to their generally low thermalconductivity. Such foams can be used, for example, as outer wallinsulation of residential and commercial buildings, shipping containers(e.g., tractor trailers, rail cars, shipping containers etc.) andpipelining, among other things. Unfoamed polyurethane materials can alsobe used for coatings, adhesives, and sealants.

The aromatic content of aromatic polyester polyols derived from PET areknown to contribute to the strength, stiffness, and thermal stability ofthe polyurethane product. RPUFs generated from aromatic polyesterpolyols have been shown to exhibit excellent overall performance ininsulation applications. Thermal stability of RPUFs depends on thepolyol structure, and aromatic polyols can be superior over aliphaticpolyols from this point of view. Previously introduced aromaticpolyester polyether polyols based on terephthalic acid or phthalicanhydride have a high content of aromatic fragments, for example, aboutaround 20%. The presence of aromatic fragments in the structure ofpolyols has been shown to enhance many properties of RPUF enabling goodmechanical characteristics, high thermal stability, resistance to majorchemical solvents, and low flammability. Nonetheless, the prevailingprice charged for existing RPUFs generated from prior art aromaticpolyester polyols makes this material much less desirable than that offoamed polystyrene or mineral wool products for commercial applications.

To this end, starting materials for both polyols for use in aromaticpolyester polyols are typically derived exclusively from petrochemicalsources. At least because the recycling of PET into useful articlesreduces some use of non-renewable materials, it would seem desirable touse such material as an upstream feedstock for polyurethane manufacture.However, the economics of such manufacture does not support this usecase. One might also infer that a price differential might be possiblefor aromatic polyester polyether polyol derived from recycled PET inthat people would be willing to pay more from polyurethane materialsderived from such a source, but this is not the case given currentmethods proposed for generation of these materials. Users are demanding“greener” products that perform equally well to existing,petroleum-derived products, but they are not typically willing to pay apremium for these products. Reduction in the price of RPUFs made fromaromatic polyester polyols could become possible by the use of PET-wastederived as raw materials.

In view of the foregoing, it would be desirable to develop methods andmaterials that could enhance the ability to use waste PET to generatechemical feedstock that can be used to generate high value materials,while still addressing the cost requirements demanded by consumers forsuch high value materials. Yet further, it would be desirable to developpolyurethane materials that exhibit improved chemical and physicalproperties. The present invention provides these and other benefits.

SUMMARY OF THE DISCLOSURE

In various aspects, the present disclosure relates to aromatic polyesterpolyether polyols having a structure that is either: (a) based on aglycerol backbone, the structure represented by a formula:

wherein each of R₁, R₂, and R₃ is independently selected from hydroxyland a structure represented by a formula:

wherein m has a value such that the aromatic polyester polyether polyolhas a suitable Brookfield Cone and Plate Viscosity; and wherein each ofn₁, n₂, and n₃ is an integer independently selected from 0, 1, 2, 3, 4,5, 6, 7, 8, and 9, provided that a sum of the values for n₁, n₂, and n₃is 1 to 9; or (b) based on a trimethylolpropane backbone, the structurerepresented by a formula:

wherein each of R₁, R₂, and R₃ is independently selected from hydroxyland a structure represented by a formula:

wherein m has a value such that the aromatic polyester polyether polyolhas a suitable Brookfield Cone and Plate Viscosity; and wherein each ofn₁, n₂, and n₃ is an integer independently selected from 0, 1, 2, 3, 4,5, 6, 7, 8, and 9, provided that a sum of the values for n₁, n₂, and n₃is 1 to 9.

In a further aspect, the present disclosure relates to an aromaticpolyester polyether polyol compositions derived from transesterificationof PET in the presence of an ethoxylated triol and, optionally, acatalyst, wherein the ethoxylated triol comprises one of: (a) glycerinhaving from 1 to 9 moles of ethoxylation; or (b) trimethylolpropanehaving from 1 to 9 moles of ethoxylation.

The aromatic polyester polyol compositions can have a Brookfield Coneand Plate Viscosity of about 5 Poise (spindle #4, 100 rpm, 60° C.) orless when the transesterification reaction is terminated.

In further aspects, the present invention relates to polyurethanematerial that are generated from a) an aromatic polyester polyetherpolyol generated according to the above-referenced transesterificationreaction of PET and an ethoxylated triol comprising either glycerin ortrimethylolpropane, wherein the triols have been modified to have from 1to 9 moles of ethoxylation; and b) an isocyanate. At least some of thePET can be derived from a recycled source. The beneficial lowviscosities of the aromatic polyester polyether polyols allow thepolyols to be workable as generated from the transesterificationreaction. Moreover, the use of recycled PET and, in someimplementations, glycerin provides a polyurethane with “green”characteristics.

The generated polyurethane can be foamed or unfoamed, and can be used asa coating on one or more sides of a substrate to provide a coatedsubstrate. The generated polyurethane can also be formed into asubstrate. The generated polyurethanes can be filled or unfilled.

The polyurethanes derived from the aromatic polyester polyether polyolsexhibit excellent physical properties, such as fire resistance,hardness, resiliency, impact resistance, and the like. Thecured-in-placed polyurethanes also provide excellent adhesion to anumber of different surface types. When formed into a substrate, thepolyurethanes can be used for structural (e.g., load bearing)applications. The polyurethanes also show good wettability to fillermaterials, and can be generated into sheets, molded shapes, and thelike.

Additional advantages of the invention will be set forth in part in thedescription that follows, and in part will be apparent from thedescription, or may be learned by practice of the invention. Theadvantages of the invention will be realized and attained by means ofthe elements and combination particularly pointed out in the appendedclaims. It is to be understood that both the foregoing generaldescription and the following detailed description are exemplary andexplanatory only and are not restrictive of the invention, as claimed.

BRIEF DESCRIPTION OF THE DRAWINGS

Further aspects of the present disclosure will be readily appreciatedupon review of the detailed description of its various aspects,described below, when taken in conjunction with the accompanyingdrawings. The components in the drawings are not necessarily to scale,emphasis instead being placed upon clearly illustrating the principlesof the present disclosure. Moreover, in the drawings, like referencenumerals designate corresponding parts throughout the several views.

FIG. 1 is a photomicrograph showing a cross-section of a foamedinventive polyurethane composition.

FIGS. 2a and 2b are cross-sectional views of one implementation of acomposite substrate coated with the foamed inventive polyurethaneadhesive coated on one surface.

FIGS. 3a and 3b are side views of one implementation of a compositesubstrate with the unfoamed inventive polyurethane adhesive coated onone surface.

FIGS. 4a and 4b are cross-sectional views of one implementation of asandwich composite panel comprising two substrates coated with thefoamed inventive polyurethane composition and adhered together.

FIG. 5 is a view of one implementation of a foamed panel generated fromthe inventive polyurethane composition.

FIG. 6 is a view of one implementation of a siding material generatedfrom the inventive polyurethane composition.

FIG. 7 is a partial cross-sectional view of a residential buildingstructure showing a plurality of uses for building materials thatincorporate or are derived from the inventive polyurethane compositions.

FIG. 8 is a partial cross-sectional view of a commercial buildingstructure showing a plurality of uses for building materials thatincorporate or are derived from the inventive polyurethane compositions.

FIG. 9 is a view of a fully coated, generic building structure.

FIG. 10 is an I-Joist partially coated with the polyurethane compositionof the present invention.

FIG. 11 is a graph of R-value measurements for foams of the presentinvention.

Additional advantages of the disclosure will be set forth in part in thedescription which follows, and in part will be obvious from thedescription, or can be learned by practice of the disclosure. Theadvantages of the disclosure will be realized and attained by means ofthe elements and combinations particularly pointed out in the appendedclaims. It is to be understood that both the foregoing generaldescription and the following detailed description are exemplary andexplanatory only and are not restrictive of the disclosure, as claimed.

DETAILED DESCRIPTION

Many aspects of the disclosure can be better understood with referenceto the Figures presented herewith. The Figures are intended toillustrate the various features of the present disclosure. Moreover,like references in the drawings designate corresponding parts among theseveral views. While several implementations may be described inconnection with the included drawings, there is no intent to limit thedisclosure to the implementations disclosed herein. To the contrary, theintent is to cover all alternatives, modifications, and equivalents.

Before the present disclosure is described in greater detail, it is tobe understood that this disclosure is not limited to particular aspectsdescribed, and as such may, of course, vary. It is also to be understoodthat the terminology used herein is for the purpose of describingparticular aspects only, and is not intended to be limiting. The skilledartisan will recognize many variants and adaptations of the aspectsdescribed herein. These variants and adaptations are intended to beincluded in the teachings of this disclosure and to be encompassed bythe claims herein.

All publications and patents cited in this specification are hereinincorporated by reference as if each individual publications or patentwere specifically and individually indicated to be incorporated byreference and are incorporated herein by reference to disclose anddescribe the methods and/or materials in connection with which thepublications are cited. The citation of any publication is for itsdisclosure prior to the filing date and should not be construed as anadmission that the present disclosure is not entitled to antedate suchpublications by virtue of prior disclosure. Further, the dates ofpublications provided could be different from the actual publicationsdates that may need to be independently confirmed.

Any recited method can be carried out in the order of events recited orin any other order that is logically possible. That is, unless otherwiseexpressly stated, it is in no way intended that any method or aspect setforth herein be construed as requiring that its steps be performed in aspecific order. Accordingly, where a method claim does not specificallystate in the claims or descriptions that the steps are to be limited toa specific order, it is no way intended that an order be inferred, inany respect. This holds for any possible non-express basis forinterpretation, including matters of logic with respect to arrangementof steps or operational flow, plain meaning derived from grammaticalorganization or punctuation, or the number or type of aspects describedin the specification.

Although any methods and materials similar or equivalent to thosedescribed herein can also be used in the practice or testing of thepresent disclosure, the various methods and materials suitable for usewith the various inventions disclosed herein are now described.Functions or constructions well-known in the art may not be described indetail for brevity and/or clarity.

Prior to describing the various aspects of the present disclosure, thefollowing definitions are provided and should be used unless otherwiseindicated. Additional terms may be defined elsewhere in the presentdisclosure.

General Definitions

As used herein, “comprising” is to be interpreted as specifying thepresence of the stated features, integers, steps, or components asreferred to, but does not preclude the presence or addition of one ormore features, integers, steps, or components, or groups thereof.Moreover, each of the terms “by”, “comprising,” “comprises”, “comprisedof,” “including,” “includes,” “included,” “involving,” “involves,”“involved,” and “such as” are used in their open, non-limiting sense andmay be used interchangeably. Further, the term “comprising” is intendedto include examples and aspects encompassed by the terms “consistingessentially of” and “consisting of.” Similarly, the term “consistingessentially of” is intended to include examples encompassed by the term“consisting of.”

As used in the specification and the appended claims, the singular forms“a,” “an” and “the” include plural referents unless the context clearlydictates otherwise. Thus, for example, reference to “an aromaticpolyester polyether polyol,” “a polyethylene terephthalate,” or “a rigidpolyurethane foam,” includes, but is not limited to, two or more sucharomatic polyester polyether polyols, polyethylene terephthalates, orrigid polyurethane foams, and the like.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this disclosure belongs. It will be further understoodthat terms, such as those defined in commonly used dictionaries, shouldbe interpreted as having a meaning that is consistent with their meaningin the context of the specification and relevant art and should not beinterpreted in an idealized or overly formal sense unless expresslydefined herein.

As used herein, the terms “about,” “approximate,” “at or about,” and“substantially” mean that the amount or value in question can be theexact value or a value that provides equivalent results or effects asrecited in the claims or taught herein. That is, it is understood thatamounts, sizes, formulations, parameters, and other quantities andcharacteristics are not and need not be exact, but may be approximateand/or larger or smaller, as desired, reflecting tolerances, conversionfactors, rounding off, measurement error and the like, and other factorsknown to those of skill in the art such that equivalent results oreffects are obtained. In some circumstances, the value that providesequivalent results or effects cannot be reasonably determined. In suchcases, it is generally understood, as used herein, that “about” and “ator about” mean the nominal value indicated ±20%, ±15%, ±10%, ±9%, ±8%,±7%, ±6%, or ±5% of the specified value, e.g., about 1″ refers to therange of 0.8″ to 1.2″, 0.8″ to 1.15″, 0.9″ to 1.1″, 0.91″ to 1.09″,0.92″ to 1.08″, 0.93″ to 1.07″, 0.94″ to 1.06″, or 0.95″ to 1.05″,unless otherwise indicated or inferred. It is understood that where“about,” “approximate,” or “at or about” is used before a quantitativevalue, the parameter also includes the specific quantitative valueitself, unless specifically stated otherwise.

Any ratios, concentrations, amounts, and other numerical data can beexpressed herein in a range format. Such a range format is used forconvenience and brevity, and thus, should be interpreted in a flexiblemanner to include not only the numerical values explicitly recited asthe limits of the range, but also to include all the individualnumerical values or sub-ranges encompassed within that range as if eachnumerical value and sub-range is explicitly recited. To illustrate, aconcentration range of “about 0.1% to about 5%” should be interpreted toinclude not only the explicitly recited concentration of about 0.1 wt %to about 5 wt %, but also include individual concentrations (e.g., 1%,2%, 3%, and 4%) and the sub-ranges (e.g., 0.5%, 1.1%, 2.2%, 3.3%, and4.4%) within the indicated range. Where the stated range includes one orboth of the limits, ranges excluding either or both of those includedlimits are also included in the disclosure, e.g., the phrase “x to y”includes the range from ‘x’ to ‘y’ as well as the range greater than ‘x’and less than ‘y’. The range can also be expressed as an upper limit,e.g., ‘about x, y, z, or less’ and should be interpreted to include thespecific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as theranges of ‘less than x’, less than y’, and ‘less than z’. Likewise, thephrase ‘x, y, z, or greater’ should be interpreted to include thespecific ranges of ‘about x’, ‘about y’, and ‘about z’ as well as theranges of ‘greater than x’, greater than y’, and ‘greater than z’. Insome aspects, the term “about” can include traditional roundingaccording to significant figures of the numerical value. In addition,the phrase “about ‘x’ to ‘y’” includes “about ‘x’ to about “y.”

The term “substantially” is meant to permit deviations from thedescriptive term that do not negatively impact the intended purpose. Alldescriptive terms used herein are implicitly understood to be modifiedby the word “substantially,” even if the descriptive term is notexplicitly modified by the word “substantially.”

The term “hydroxyl number” as used herein is defined as the number ofmilligrams of potassium hydroxide required for the completeneutralization of the hydrolysis product of a fully acetylatedderivative prepared from one gram of a polyol or a mixture of polyols.The term “hydroxyl number” is also defined by the equation:

${{OHV} = \frac{56.1 \times 1000 \times F}{M.W.}},$

where OHV is the hydroxyl number (of the polyol or polyol blend), F isthe average functionality (i.e., the average number of active hydroxylgroups per molecule of the polyol or polyol blend), and M.W. is theaverage molecular weight of the polyol or polyol blend. In someimplementations, ASTM 4247-16, Test A can be used.

The term “closed-cell foam,” as used herein, refers to a foam that isessentially fluid impermeable because the cells are not substantiallyinterconnected, e.g., a blown foam having a closed-cell content of about50 volume %, 60 volume %, 70 volume %, 75 volume %, 80 volume %, 85volume %, 90 volume %, or more, e.g., essentially 100 volume % of thecells can be closed.

As used herein, the term “effective amount” refers to an amount that issufficient to achieve the desired modification of a physical property ofthe composition or material. For example, an “effective amount” of acoating on a substrate is that amount suitable to provide the desiredend result, such as impact resistance, hardness, R-value, and the like.

As used herein, the terms “optional” or “optionally” means that thesubsequently described event or circumstance can or cannot occur, andthat the description includes instances where said event or circumstanceoccurs and instances where it does not.

It is understood that when non-metric or SI units are used herein, thatthey are in U.S. Customary Measures, e.g., as set forth by the NationalInstitute of Standards and Technology, Department of Commerce, UnitedStates of America in publications such as NIST HB 44, NIST HB 133, NISTSP 811, NIST SP 1038, NBS Miscellaneous Publication 214, and the like.The units in U.S. Customary Measures are understood to includeequivalent dimensions in metric and other units (e.g., a dimensiondisclosed as “1 inch” is intended to mean an equivalent dimension of“2.5 cm”; a unit disclosed as “1 pcf” is intended to mean an equivalentdimension of 0.157 kN/m³; or a unit disclosed 100° F. is intended tomean an equivalent dimension of 37.8° C.; and the like) as understood bya person of ordinary skill in the art.

Aromatic Polyester Polyether Polyols

In a first aspect, the invention comprises an aromatic polyesterpolyether polyol generated, in one aspect, from transesterification ofpolyethylene terephthalate (“PET”) in a transesterification reactionconducted in the presence of a low molecular weight triol material,wherein the low molecular weight triol comprises either glycerin ortrimethylolpropane, and wherein each of the glycerin ortrimethylolpropane, independently, has been modified with from 1 to 9moles of ethylene oxide according to known methodology. Yet further,each of the glycerin or trimethylolpropane, independently, has beenmodified with 1 or about 2 or about 3 or about 4 or about 5 or about 6or about 7 or about 8 moles or 9 moles of ethylene oxide, wherein anyvalue can form an upper or lower ethylene oxide modification endpoint,as appropriate. Still further, the inventive aromatic polyesterpolyether polyol is derived from transesterification of PET withtrimethylolpropane or glycerin consisting essentially of 1 to 9 moles ofethoxylation, or, in more specific implementations, 1 or 2 or 3 or 4 or5 or 6 or 7 or 8 or 9 moles of ethoxylation.

The inventors herein have surprisingly discovered that the use ofglycerin or trimethylolpropane having the specified degree ofethoxylation, and no more or no less, provides a collection ofbeneficial properties in both the inventive aromatic polyester polyetherpolyol, as well as the generated polyurethane. The generatedpolyurethane can be foamed or unfoamed, and used as a coating for asubstrate or as a substrate itself. Transesterification of the PET withthe low molecular weight hydroxyl-containing materials of glycerin ortrimethylolpropane having the specified degree of ethoxylation has beenfound to provide a polyol having beneficially low viscosities so as toallow both efficient workability and polyurethane reactioncharacteristics between and among the hydroxyls in the generated polyolmaterials and the reactive moieties of the isocyanate materials, as wellas application efficacy onto a substrate when used as a coating.

Without being bound by theory, the inventors herein hypothesize thataddition of from 1 to 9 moles of ethoxylation to either glycerin ortrimethylolpropane has an effect of moving reactive hydroxyl groups outfrom a branching center allowing for a PET transesterification reactionto suitably occur. At about 5 to 6 moles of ethoxylation, the number ofsterically hindered hydroxyl groups could be minimized to reduceinterference with the transesterification reaction. At the lower amountsof ethoxylation, for example, 1, 2, 3 or 4 moles, transesterificationstill occurs, but to a lesser extent. However, when the generated 1, 2,3, or 4 moles of ethoxylated glycerin or trimethylolpropane-reactedaromatic polyester polyether polyol material is reacted with isocyanate,the secondary/sterically hindered hydroxyl groups can be reacted, andthus the hindered branching center can be preserved, although some ofthe attachment groups may now comprise esters. As least some of thedifferences in the resulting polyurethane may be seen in impactresistance, with PET transesterification with triols having the lowerethoxylation amounts appearing to exhibit at least modestly lower impactresistance than polyurethanes generated from transesterification withthe triols having 5 or 6 or 7 moles of ethoxylation. The inventors haveobserved that when triols having 5, 6, and 7 moles of ethoxylation areused, polyurethanes exhibiting increased impact resistance good surfacehardness can be generated. At ethoxylation amounts of greater than 7moles and up to 9 moles, the generated polyurethanes appear to lose somesurface hardness and become more flexible, however, other desirableproperties may be exhibited. The properties of polyurethanes made withthe inventive aromatic polyester polyether polyols are discussed furtherhereinafter.

A significant aspect of the present invention comprises the ability touse at least some amount of PET that is derived from a recycled source,generally in the form of flakes or pellets, to generate at least some ofthe hydroxyl functionality for reaction with the isocyanate. As notedpreviously, there is an abundance of PET in waste streams throughout theglobe. The present invention provides a heretofore unavailable use for anot insignificant amount of such waste material as a chemical feedstockto generate valuable materials, such as polyurethanes. Such recycledmaterial can be derived from pre-consumer or post-consumer use. A commonsource for recycled PET is pre- or post-consumer waste streams derivedfrom plastic bottles or other containers. Such PET can be colorless orcontain dyes (e.g., green, blue, or other colors) or can be mixtures ofthese. A minor proportion of organic or inorganic foreign matter (e.g.,paper, other plastics, glass, and metal) can be present, which can beseparated out prior to the transesterification reaction. At a minimum,however, recycled PET will include at least some artifacts of the prioruse. For example, for PET oligomers derived from post-consumer wastewill exhibit at least some of the characteristics imparted by theprocessing of the PET into the product in which it was previously used,such as blow molding for bottles, stretching for fibers, etc. Thus, PEToligomers generated in the transesterification reaction will include atleast some artifacts of a previous mechanical treatment, such as reducedI.V, as discussed hereinafter. Moreover, it typically would not be costeffective to remove all additives from the PET prior to use thereof,especially since colorants, UV scavengers, etc, that are typicallyincluded in a first use process for PET may position themselves betweenpolymeric chains during the first processing step and, thus, will differat least in this regard from an aromatic polyester polyether polyolgenerated from virgin raw chemical feedstock.

A desirable type of recycled PET is “flake” PET, from which many, butnot all, of the common impurities present in scrap PET bottles have beenremoved in advance. Another desirable source of recycled PET ispelletized PET. In the present invention, at least about 5, 10, 20, 30,40, 50, 60 or 70% or more of recycled PET can be used to generate thearomatic polyester polyether polyols. Yet further, at least some virginPET can be used. A mixture of virgin and recycled PET can be used.

In a significant implementation of the present invention, theethoxylated glycerin can be at least partially derived from asustainable, or non-petroleum source, such as vegetable or animalsources. Glycerin, a simple triol, has been utilized as afunctionality-enhancing additive both in neat form and in an ethoxylatedform in either the PET depolymerization process or post-depolymerizationprocess to synthesize aromatic polyester polyols for polyurethane foamapplications, but there is no indication that this material having thespecified ethoxylation amount of 1 to 9 moles has been used in as thesole or primary transesterification material for PET. In this regard,when ethoxylated glycerin is utilized in the transesterificationreaction, the reaction vessel comprises substantially no other materialthat can participate in the transesterification reaction at the startthereof.

Yet further, upcycled glycerol from biodiesel manufacture can be used tofurther improve the environmental profile of the polyurethanes herein.As would be recognized, glycerol is a major byproduct in the biodieselmanufacturing process. In general, for every 100 pounds of biodieselproduced, approximately 10 pounds of crude glycerol are created. As thebiodiesel industry is rapidly expanding, a glut of crude glycerol isbeing created, and use of such waste to make the inventive aromaticpolyester polyether polyols can be beneficial.

In further implementations, at least some of the inventive polyol can begenerated by reaction of terephthalic acid in the presence of thespecifically modified glycerin or trimethylolpropane as discussed hereinabove to provide an aromatic polyester polyether polyol directly fromraw materials, as opposed to being generated from glycolysis of PET in atransesterification process.

In some aspects, the aromatic polyester polyether polyols of the presentinvention comprise substantially no imide groups. Yet further, thearomatic polyester polyether polyols of the present invention haveessentially no acid groups that can react with an isocyanate containingmaterial. In this regard, the aromatic polyester polyether polyols ofthe present invention have an acid value of less than about 1.0 or 0.5,or 0.1 mg KOH/g. Still further, substantially all isocyanate reactivegroups on the aromatic polyester polyether polyols are comprised ofhydroxyl groups. In further aspects, the aromatic polyester polyetherpolyols comprise essentially no aldehyde groups. The aromatic polyesterpolyether polyols suitable for use in the present invention exhibitsubstantial moisture stability. In this regard, the prevalence ofaromatic ester groups in the inventive polyol can reduce the reactivitywith water in the generated polyurethane, at least because aromaticester groups are substantially more resistant to hydrolysis.

In some aspects, it can be beneficial to ensure that the PET being usedto generate the inventive polyols is substantially free of metaladditives. In this regard, the metallic content of the PETs can be lessthan about 1% or less than about 0.1% or less than about 0.01%. Stillfurther, the PETs used herein can be derived from a source of PET thatcontains no metallic additives, exclusive of the catalyst used togenerate the PET.

The amount of PET used in the transesterification reaction, on a weightpercentage of the total amount of material in the reaction, can be fromabout 5% to about 50%, from about 10 to about 35%, or from about 15 toabout 30%. Still further, the amount of PET used in thetransesterification reaction is about 5, 10, 15, 20, 30, 35, 40, 45, 50,55, 60 or 65% by weight, where any value can form an upper or lowerendpoint, as appropriate. Yet further, the amount of PET used in thetransesterification reaction is no more than 65% by weight. Accordingly,the amount of ethoxylated triol present in the transesterificationreaction can be in the amount needed to add up to 100% by weight. (Notethat the catalyst, if any, may not be incorporated in the weight percentcalculations.) Still further, the ratio of PET to ethoxylated triolhaving from 1 to 9 moles of ethoxylation can be about 10:90, 20:80,30:70; 40:60, 50:50, or 60:40. As noted, at least some of the PET usedcan be from a recycled source.

In one example methodology for the transesterification reaction, the PETand glycerin or trimethylolpropane having the specified degree ofethoxylation are heated, optionally in the presence of a catalyst, togive one or more intermediates comprising a polyol and aterephthalate-containing hydroxyl functional component. The reactionvessel can be charged at the start of the transesterification reactionwith substantially only the following ingredients: PET, glycerin ortrimethylolpropane having the specified degree of ethoxylation and,optionally, catalyst. Once the transesterification reaction is underway,glycols present in the reaction vessel may include the ethoxylatedglycerin or trimethylolpropane and ethylene glycol generated fromglycolysis of the PET. Heating is advantageously performed attemperatures of from about 160° C. to about 260° C., or from about 180°C. to about 240° C. Yet further, heating can be at from about 160, 180,200, 220, 240, 260, 280, or 300° C., where any value can form an upperor lower endpoint, as appropriate.

Transesterification catalysts, if used, suitable for use herein includetitanium, zinc, antimony, germanium, zirconium, manganese, or othermetals. Specific examples include titanium alkoxides (e.g., tetrapropyltitanate), titanium(IV) phosphate, zirconium alkoxides, zinc acetate,lead acetate, cobalt acetate, manganese(II) acetate, antimony trioxide,germanium oxide, or the like, and mixtures thereof. Catalysts that donot significantly promote isocyanate reaction chemistries can beadvantageously used. The amount of catalyst used is typically from about0.005 to about 5 wt. %, or from about 0.01 to about 1 wt. % or fromabout 0.02 to about 0.7 wt. %, based on the total amount of polyol beingprepared. In some implementations, the catalyst may be omitted, such aswhen recycled PET is used. In this situation, residual catalyst in thePET can operate as the catalyst for the transesterification reaction.

The aromatic polyester polyether polyol preparation procedure is anotable feature of the present invention, at least in respect to therelatively low viscosities generated from the transesterificationprocess, namely a Brookfield Cone and Plate Viscosity of 5 Poise or less(spindle #4, 60° C., 100 rpm). In this regard, and as set forth in theExamples hereinafter, the ethoxylated glycerin or trimethylolpropanehaving the specified degree of ethoxylation of 1 to 9 moles is heated ina 250 ml flask with PET to allow the mixture in the reaction vessel toreach at least about 220° C. or about 230° C. after about 45, or 60, or90, or 120 minutes. When this temperature is reached, the reactionmixture can be examined to determine the whether the transesterificationreaction is suitably underway to generate the inventive aromaticpolyester polyether polyol. To this end, several drops of thePET/ethoxylated triol material in the reaction vessel can be placed on aclean dry surface. If the mixture shows a cloudy appearance on thesurface after 10 minutes, an indication that the PET has not beensuitably transesterified will be generated, and the reaction can beallowed to continue, and additional testing can be conducted at 10minute increments. This is termed the “Clear Pill Test.” Heating of thereaction vessel can be continued while the one or more Clear Pill Testsis being conducted. When the removed PET/ethoxylated material remainsclear on the plate for about 10 minutes, a first Brookfield Cone andPlate Viscosity of the PET/ethoxylated triol material in the reactionvessel can be generated. For PET transesterified with ethoxylatedglycerin, the first viscosity can be from about 2.7 to about 3.2 Poise(spindle #4, 60° C., 100 rpm). For PET transesterified with ethoxylatedtrimethylolpropane, the first tested Brookfield Cone and Plate Viscositycan be from about 3.7 to about 4.2 Poise (spindle #4, 60° C., 100 rpm).This first tested Brookfield Cone and Plate Viscosity is an indicationthat the transesterification reaction is suitably ongoing, and thereaction can be stopped at that point. Alternatively, the reactionvessel can be allowed to remain under heat for about 10, or about 15, orabout 30 more minutes to obtain a second Brookfield Cone and PlateViscosity. A suitable aromatic polyester polyether polyol for use willexhibit a second Brookfield Cone and Plate Viscosity can be generated ofabout 3.2 to about 3.8 Poise (spindle #4, 60° C., 100 rpm) for aninventive polyol generated from ethoxylated glycerin, and from about 4.0to about 5.0 Poise (spindle #4, 60° C., 100 rpm) for an inventive polyolgenerated from ethoxylated trimethylolpropane.

In this regard, the heating of ethoxylated glycerin or ethoxylatedtrimethylolpropane, wherein each have the specified degree ofethoxylation, in the presence of PET in accordance with the inventiveprocedure generates a specific aromatic polyester polyether polyol endproduct. Notably, the ability to characterize the product of thetransesterification reaction in relation to a beneficial viscosity rangethat indicates the suitable generation of the inventive polyols (and theend of the transesterification reaction) provides a relatively simpleprocess for use in varied downstream processes.

While the above description is relevant to a small, bench scaleoperation, with small volumes of reactants. It would be appreciated thatlarger volumes of reactants would be appropriate for commercial uses. Inthis regard, variations in the reaction conditions may be appropriate.Nonetheless, the use of the relatively simple tests of whether a “ClearPill” and whether the first and second viscosity tests that indicate thegeneration of the inventive aromatic polyester polyether polyol canremove uncertainties that often result from scaling up for commercialuse.

Moreover, differences in the Intrinsic Viscosity (“I.V.”) of the PET mayresult in variations in the aromatic polyester polyether polyolgenerated from the transesterification reaction. As would beappreciated, I.V. is a measure of the polymers molecular weight andtherefore reflects the material's melting point, crystallinity andtensile strength. It would be appreciated that heating of PET, as occurswhen a PET is processed into products, may result in a lower I.V. for arecycled PET as compared to the I.V. for that same PET that is generatedfrom a virgin source. As such, an aromatic polyester polyether polyolgenerated at all or in part from a recycled PET source may trend towardthe lower ends of the respective viscosity ranges. Such variations canreadily be determined by one of ordinary skill in the art.

In accordance with the transesterification process of the presentinvention, the aromatic polyester polyether polyols can be characterizedin a number of manners.

In a first characterization, the aromatic polyester polyether polyolscomprise branched polyols suitable for reaction with isocyanate, whereinthe polyols are prepared via transesterification of a glycerin ortrimethylolpropane having 1 to 9 moles of ethoxylation with PET with thefirst reaction product resulting in terephthalate moieties reacted to aflexible branching center. Ethoxylated glycerin or trimethylolpropaneare hypothesized to “activate” the terminal hydroxyl groups on thesetriols for chain insertion in the PET during the transesterificationreaction.

In a further characterization, the invention comprises aromaticpolyester polyether polyols that are the reaction product of an ethyleneoxide modified glycerin or trimethylolpropane having a degree ofethoxylation of 1 to 9 moles with polyethylene terephthalate throughtransesterification, wherein the reaction is judged to be substantiallycompleted when the material in the reaction vessel has a viscositycharacteristic(s) as set out hereinabove. In this regard, the product ofthe transesterification process would appear to be a mixture ofdifferent molecular weight PET-related materials therein. The inventorshypothesize that the clarity of the materials at this stage may conformto a mixture of materials having about 6-7 PET chain length, but theycould also be shorter or longer, where such chain lengths can beconfirmed by Differential Scanning Calorimetry, Gel PermeationChromatography, or any other suitable analytical technique.

The aromatic polyester polyether polyols derived from the referencedtransesterification reaction can further be characterized as anoligomeric mixture of branched, hydroxyl terminated moieties prepared bythe transesterification of PET with an ethylene oxide modified glycerinand trimethylolpropane having 1 to 9 moles of ethoxylation, having oneor more viscosity characteristics as described hereinabove.

Yet further, the aromatic polyester polyether polyols can becharacterized as a mixture of terephthalate esters prepared by thetransesterification of PET with an ethylene oxide modified glycerin ortrimethylolpropane having 1 to 9 moles of ethoxylation, having one ormore viscosity characteristics as described hereinabove.

In various aspects, a disclosed aromatic polyester polyether polyol hasa structure based on a glycerol backbone, the structure represented by aformula:

wherein each of R₁, R₂, and R₃ is independently selected from hydroxyland a structure represented by a formula:

wherein m has a value such that the aromatic polyester polyether polyolhas a first Brookfield Cone and Plate Viscosity of about 2.7 to about3.2 Poise (Spindle #4, 60° C., 100 rpm); wherein the first BrookfieldCone and Plate Viscosity is as defined herein above; and wherein each ofn₁, n₂, and n₃ is an integer independently selected from 0, 1, 2, 3, 4,5, 6, 7, 8, and 9, provided that a sum of the values for n₁, n₂, and n₃is 1 to 9.

In various aspects, the disclosed aromatic polyester polyether polyolshave a structure based on a glycerol backbone, the structure representedby a formula:

wherein each of R₁, R₂, and R₃ is independently selected from hydroxyland a structure represented by a formula:

wherein m has a value such that the aromatic polyester polyether polyolhas a second Brookfield Cone and Plate Viscosity of about 3.2 to about3.8 Poise (Spindle #4, 60° C., 100 rpm); wherein the second BrookfieldCone and Plate Viscosity is as defined herein above; and wherein each ofn₁, n₂, and n₃ is an integer independently selected from 0, 1, 2, 3, 4,5, 6, 7, 8, and 9, provided that a sum of the values for n₁, n₂, and n₃is 1 to 9.

In a further aspect, a disclosed aromatic polyester polyether polyolscan have a structure based on a glycerol backbone, the structurerepresented by a formula:

wherein m, n₁, n₂, and n₃ having the meaning as specified herein.

In a further aspect, a disclosed aromatic polyester polyether polyolscan have a structure based on a glycerol backbone, the structurerepresented by a formula:

wherein m, n₁, n₂, and n₃ having the meaning as specified herein.

In a further aspect, a disclosed aromatic polyester polyether polyolscan have a structure based on a glycerol backbone, the structurerepresented by a formula:

wherein m, n₁, n₂, and n₃ having the meaning as specified herein; andwherein the value of each occurrence of m can vary independently fromanother occurrence of m.

In a further aspect, a disclosed aromatic polyester polyether polyolscan have a structure based on a glycerol backbone, the structurerepresented by a formula:

wherein m, n₁, n₂, and n₃ having the meaning as specified herein; andwherein the value of each occurrence of m can vary independently fromanother occurrence of m.

In various aspects, the disclosed aromatic polyester polyether polyolshave a structure based on a trimethylolpropane (or alternativelyreferred to herein as “TMP”) backbone, the structure represented by aformula:

wherein each of R₁, R₂, and R₃ is independently selected from hydroxyland a structure represented by a formula:

wherein m has a value such that the aromatic polyester polyether polyolhas a first Brookfield Cone and Plate Viscosity of about 3.7 to about4.2 Poise (Spindle #4, 60° C., 100 rpm); wherein the first BrookfieldCone and Plate Viscosity is as defined herein above; and wherein each ofn₁, n₂, and n₃ is an integer independently selected from 0, 1, 2, 3, 4,5, 6, 7, 8, and 9, provided that a sum of the values for n₁, n₂, and n₃is 1 to 9.

In various aspects, the disclosed aromatic polyester polyether polyolshave a structure based on a TMP backbone, the structure represented by aformula:

wherein each of R₁, R₂, and R₃ is independently selected from hydroxyland a structure represented by a formula:

wherein m has a value such that the aromatic polyester polyether polyolhas a second Brookfield Cone and Plate Viscosity of about 4.0 to about5.0 Poise (Spindle #4, 60° C., 100 rpm); wherein the second BrookfieldCone and Plate Viscosity is as defined herein above; and wherein each ofn₁, n₂, and n₃ is an integer independently selected from 0, 1, 2, 3, 4,5, 6, 7, 8, and 9, provided that a sum of the values for n₁, n₂, and n₃is 1 to 9.

In a further aspect, a disclosed aromatic polyester polyether polyolscan have a structure based on a TMP backbone, the structure representedby a formula:

wherein m, n₁, n₂, and n₃ having the meaning as specified herein.

In a further aspect, a disclosed aromatic polyester polyether polyolscan have a structure based on a TMP backbone, the structure representedby a formula:

wherein m, n₁, n₂, and n₃ having the meaning as specified herein.

In a further aspect, a disclosed aromatic polyester polyether polyolscan have a structure based on a TMP backbone, the structure representedby a formula:

wherein m, n₁, n₂, and n₃ having the meaning as specified herein; andwherein the value of each occurrence of m can vary independently fromanother occurrence of m.

In a further aspect, a disclosed aromatic polyester polyether polyolscan have a structure based on a TMP backbone, the structure representedby a formula:

wherein m, n₁, n₂, and n₃ having the meaning as specified herein; andwherein the value of each occurrence of m can vary independently fromanother occurrence of m.

Still further, a measured hydroxyl number for the generated polyol canbe a function of not only the aromatic polyester polyether polyol (whichcan be a mixture of hydroxyl-functional PET oligomers), but also ofother measurable hydroxyl functionality of ethylene glycol that may bepresent in the reaction vessel. If ethylene glycol is substantiallyremoved from the reaction vessel or a hydroxyl functional material isadded to the reaction vessel, a measured hydroxyl number willsubstantially be a function of the total amount of measurable hydroxylfunctionality present in the composition from the PET oligomers.

In yet a further characterization, the present invention comprises acomposition that comprises a material conforming to the above referencedformulas, wherein the composition can comprise at least some ethyleneglycol that is generated in the transesterification reaction.

Still further, the vessel is substantially not pressurized during thetransesterification process, and no condensation apparatus need be used.As would be recognized, such a process can greatly simplify the aromaticpolyester polyether polyols manufacturing process: the minimum stepsthat are required include placing the appropriate amounts of PET andethoxylated material in a reaction vessel or “pot” and heating themixture with stirring for the appropriate time. The cooking process ofthe present invention is therefore very simple. In this regard, in someimplementations, the aromatic polyester polyether polyols of the presentinvention can comprise at least some free ethylene glycol therein at theend of the process. Such ethylene glycol can then be available to reactwith the isocyanate. Without being bound by theory, it is hypothesizedthat, even though the transesterification reaction is conducted at atemperature above which ethylene glycol boils (e.g., 197° C.), thismaterial may not effectively boil off under the conditions of thereaction, and therefore at least some may remain in the reaction vesselduring the transesterification, as well as afterwards. To this end, itis believed that, in some implementations, there is at least someethylene glycol present in the aromatic polyester polyether polyols atthe completion of the transesterification reaction.

In some implementations, such as during or subsequent to thetransesterification of the PET, ethylene glycol can be removed from thereaction vessel prior to use of the aromatic polyester polyether polyolsto generate the polyurethane materials discussed hereinafter. Thetransesterification reaction is generally conducted at a highertemperature than at which ethylene glycol boils (e.g., 197° C.),accordingly some ethylene glycol will be boiled off during thetransesterification reaction. Removal at least some of the ethyleneglycol from the transesterification reaction environment, either duringor after completion, has been observed to allow harder coatings to begenerated for the polyurethane, perhaps due to the lower hydroxylcontent present in the generated polyols. In some aspects, the amount ofethylene glycol present in the aromatic polyester polyether polyolprovided for use can be below about 2% or below about 1%. If removed,ethylene glycol can be removed from the polyol component using knownmethods. For example, an overhead condenser can be used to removeethylene glycol and water that can be present in the PET. A nitrogenpurge or sparge may be applied to remove ethylene glycol. If a highermolecular weight aromatic polyester polyether polyol is desired, moreethylene glycol can be removed, for example.

It has been observed that use of an increase in the amount of PET in thetransesterification reaction can result in a lower hydroxyl number forthe inventive aromatic polyester polyether polyols, whereas a loweramount of PET can result in a higher hydroxyl number. It has furtherbeen observed that an increase in PET amount can result in a higherviscosity for the aromatic polyester polyether polyols, however, suchhigher viscosities can be managed with slight heating prior to use, asdiscussed elsewhere herein.

The inventive aromatic polyester polyether polyols can further bedifferentiated because they are flowable liquids at temperatures belowabout 40° C., or about 50° C., or about 60° C., or about 70° C., orabout 80° C. In other implementations, the inventive aromatic polyesterpolyether polyols are advantageously flowable liquids under ambient orslightly elevated conditions, which is a distinct advantage forformulating polyurethanes.

As would be recognized, the viscosity of the polyols can vary asfunction of the molecular weight, with the greater the degree oftransesterification/depolymerization typically being associated withlower viscosities. In this regard, the transesterification process canbe terminated when the viscosity of the aromatic polyester polyetherpolyol is observed to be from about 3.0 to about 6.0, or from about 4.0to about 5.5, or from about 4.5 to about 5.0 Poise, as measured by aCone and Plate Brookfield viscometer at 100 rpm using at 60° C. usingspindle #4, or at about 70° C. if the aromatic polyester polyetherpolyols is too viscous at 60° C., such as was seen with 50% PET/50%glycerin having 2 moles of ethoxylation, for example. Yet further, theviscosity of the aromatic polyester polyether polyol when thetransesterification reaction is terminated can be about 2.0, 2.5, 3.0,3.5, 4.0, 4.5, 5.0, 5.5, 6.0, 6.5, 7.0, 7.5 or 8.0 Poise, as measured bythe stated Brookfield parameters, where any value can be used as anupper or lower endpoint as appropriate.

At the very least, this viscosity property is a surprising improvementin relation to aromatic polyester polyether polyols in the prior art inthat certain properties present with this type of polyol (e.g., enhancedflame retardance) can be leveraged to generate polyurethane materialshaving useful properties substantially without the need to heat thepolyols above about 70° C. and/or add viscosity modifiers to make themworkable under the conditions of use. Moreover, when recycled PET andethoxylated glycerin is used, the present invention generatespolyurethanes that have heretofore unrealized “green” characteristics.

When prepared from recycled PET, the aromatic polyester polyether polyolmay comprise fillers, colorants, etc. that were not removed previously.Accordingly, in some aspects, the aromatic polyester polyether polyolcan be treated with a decolorizing agent and/or be subjected to afiltering step. Such methodologies are well-known to those of skill inthe art. Alternatively, the native color of the aromatic polyesterpolyether polyol can be left in therein, which will result in thefinished polyurethane having a “muddy” color, for example. Such color istypically irrelevant when the polyurethane is used on an interiorsurface. However, when the polyurethane is used on an exterior/visiblesurface, the polyurethane is tintable or it can be painted, as furtherdiscussed herein.

The inventive aromatic polyester polyether polyols can be usedsubstantially immediately after generation, or they can be stored,transported etc. In this regard, the aromatic polyester polyetherpolyols are storage stable when kept in substantially air tight andlight proof containers. Such storage stability is exhibited, forexample, at least in the form of the viscosities set out hereinabove.

Additives can be added to the aromatic polyester polyether polyolssubstantially after completion of the PET transesterification—that is,when the target viscosity characteristics are obtained—and prior toreaction with the isocyanate material, as would be appreciated by thoseof ordinary skill in the art. In this regard, the polyol component mayalso comprise a silicone-containing material, such as a siliconesurfactant. Typically, silicone surfactants can be included to moderatecell size and shape of a foam comprising the reaction product of theinventive aromatic polyester polyether polyol and the isocyanatecomponent. If utilized, the silicone surfactant may be utilized in anamount of from about 0.1 to about 10, about 0.5 to about 9, about 1 toabout 8, or about 2 to about 7, parts by weight, each based on 100 partsby weight of the inventive aromatic polyester polyether polyol.

The inventive aromatic polyester polyether polyol may also comprise aplasticizer added after the generation of the polyol from thetransesterification process. It is believed that the plasticizer canreduce cracking of the rigid foam by softening the rigid foam therebypermitting CO₂ to escape from the rigid foam. In various aspects, theplasticizer can comprise longer chain polyethylene glycols, such as PEG400, for example. If utilized, the plasticizer may be utilized in anamount of from about 1 to about 50, about 1 to about 25, about 1 toabout 15, about 1 to about 10, or about 3 to about 7, parts by weight,each based on 100 parts by weight of the inventive aromatic polyesterpolyether polyol.

The inventive aromatic polyester polyether polyol can incorporate achain extender, wherein the chain extender is added after thesubstantial completion of the PET transesterification step. It isbelieved that the chain extender may reduce creeping of the rigid foam.Chain extenders contemplated for use in the present invention include,but not limited to, hydrazine, primary and secondary diamines, alcohols,amino acids, hydroxy acids, glycols, and combinations thereof. Specificchain extenders that are contemplated for use include, but are notlimited to, mono and di-ethylene glycols, mono and di-propylene glycols,1,4-butane diol, 1,3-butane diol, propylene glycol, dipropylene glycol,diethylene glycol, methyl propylene diol, mono, di andtri-ethanolamines, N—N′-bis-(2 hydroxy-propylaniline),trimethylolpropane, glycerine, hydroquinone bis(2-hydroxyethyl) ether,4,4′-methylene-bis(2-chloroaniline), diethyltoluenediamine,3,5-dimethylthio-toluenediamine, hydrazine, isophorone diamine, adipicacid, silanes, and combinations thereof. In various aspects, the chainextender comprises (or is) dipropylene glycol. If utilized, the chainextender may be utilized in an amount of from about 0.1 to about 20,about 1 to about 15, about 1 to about 13, or about 2 to about 12, partsby weight, each based on 100 parts by weight of the inventive aromaticpolyester polyether polyol. Glycerin or trimethylolpropane, includingethoxylated versions thereof, can also be used as modifiers of theinventive aromatic polyester polyether polyols after the completion ofthe transesterification reaction.

Isocyanates

The isocyanate with which the inventive aromatic polyester polyetherpolyol is reacted to generate the inventive polyurethane can compriseone or more of a variety of diisocyanates. An exemplary diisocyanatemonomer can include toluene diisocyanate, m-phenylene diisocyanate,p-phenylene diisocyanate, xylene diisocyanate, 4,4′-diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate,polymethylene polyphenyl diisocyanate, 3,3′-dimethyl-4,4′-biphenylenediisocyanate, 3,3′-dimethyl-4,4′-diphenylmethane diisocyanate,3,3′-dichloro-4,4′-biphenylene diisocyanate, or 1,5-naphthalenediisocyanate; their modified products, for instance,carbodiimide-modified products; or the like, or any combination thereof.Such diisocyanate monomers can be used alone or in admixture of at leasttwo kinds. In a particular example, the isocyanate component can includemethylene diphenyl diisocyanate (MDI), toluene diisocyanate (TDI),hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), or anycombination thereof. In an example, the isocyanate can include methylenediphenyl diisocyanate (MDI) or toluene diisocyanate (TDI). Inparticular, the isocyanate includes methylene diphenyl diisocyanate(MDI) or derivatives thereof.

The diisocyanate can have an average functionality in a range of about2.0 to 2.9, such as a functionality of from about 2.0 to about 2.7.Further, the diisocyanate can have an NCO content in the range of fromabout 15% to about 35%, such from about 20% to about 30%.

In one aspect, the isocyanate component can be methylene diphenyldiisocyanate (MDI). Yet further, the isocyanate component consistsessentially of MDI. In a further example, a diisocyanate can include amixture of diisocyanates, such as a mixture of modified methylenediphenyl diisocyanates. A suitable MDI for use in the invention hereinis PAPI™ 27 (Dow Chemical, Midland, Mich.), a polymeric MDI (methylenebiphenyl diisocyanate) with 31.4% NCO.

Polyurethane Compositions

As would be recognized, polyurethanes are made by the exothermicreactions between materials with two or more reactive hydroxyl (—OH)groups per molecule (diols, triols, polyols), such as the disclosedaromatic polyester polyether polyols, and isocyanates that have morethan one reactive isocyanate group (—NCO) per molecule (diisocyanates,polyisocyanates). For example, a diisocyanate reacts with a diol:

To generate a polyurethane, it is necessary to mix the right amounts ofthe two major components (polyisocyanate and polyol), which are liquidsunder reaction conditions. Heating may thus be required in use. Thereaction starts almost immediately and generates the solid polymer uponcompletion of curing. As the reaction progresses, the polyol-isocyanatemixture begins to gel in a manner that, if comprised of reactants withthe appropriate characteristics, can allow strong adhesive bonds to beformed in a cure in place operation. Completion of curing may requirethe material to be allowed to set for minutes, hours, or a few days,depending on the conditions under which the curing occurs.

The cured polyurethane composition coating can be foamed or unfoamed.When producing a foamed polyurethane, there are multiple ways togenerate a gas inside the reacting liquid mixture. The so called“chemical blowing agent” uses water that may have been added to thepolyol that reacts with some of the polyisocyanate to create carbondioxide:

OCN—R—NCO(I)+2H₂O(I)→H₂N—R—NH₂(I)+2CO₂(g)

Alternatively, in use of a “physical blowing agent,” a liquid with a lowboiling point, for example pentane, is mixed into the polyol. Theurethane reaction is exothermic and so, as it proceeds, the mixturewarms up and the pentane vaporizes. A small amount of air is dispersedthrough the mixture of polyisocyanate and polyol. This providesnucleation seeds for the multitude of gas bubbles that are producedthroughout the polymer. Heat makes the bubbles expand until thepolyurethane chemical reaction changes the liquid to solid polymer, andthe available gas pressure cannot create any further expansion.Microspheres that incorporate gas can also be used. Such blowing agentsare discussed further hereinafter.

Generation of inventive polyurethane composition can be via mechanicalimpingement spray of each of the inventive aromatic polyester polyetherpolyol component and the isocyanate components, as well as anyadditives, where such components are discussed further hereinafter.Still further, polyurethane generation can be by dynamic mixingmethodologies, pouring into or onto a mold, pultrusion, or othersuitable methodologies, as appropriate for a specific implementation.

In one aspect, the present invention comprises a polyurethane derivedfrom an aromatic polyester polyether polyol where the polyurethaneexhibits strong adhesion in an in situ polymerization process—that is,is cured-in-place—to a number of surface configurations, as discussed inmore detail hereinafter

When fully cured-in-place on a substrate surface, the adhesive strengthof the polyurethane composition is such that, for a number ofsubstrates, the adhesive bond between the substrate and thecured-in-place polyurethane coating is greater than the internalstrength of the substrate itself. In this regard, the internal bonds inthe substrate itself will break or fracture before the adhesive bondfails between the substrate and the polyurethane. For example, whencured-in-place on a wooden board and a pulling force is applied toattempt to separate the polyurethane from the substrate, the wood itselfwill break apart, and therefore fail, before the polyurethane adhesivecoating pulls away from the surface of the board.

In this regard, the inventive aromatic polyester polyether polyols arebelieved by the inventors herein to provide surprisingly efficientwetting to a wide variety of surfaces relevant to a number of industriesand applications. Without being bound by theory, it is believed that atleast some of this wettability is conferred by at least the terephthalicmoieties in the PET. This can, in turn, increase the overall contact ofthe polyol on a surface prior to substantial gelling of the aromaticpolyester polyether polyol/isocyanate mixture on the substrate surface,as well as prior to substantial completion of the curing which, in turn,improves the adhesion of the cured-in-place polyurethanes to thesubstrates.

The inventors have determined that, when cured-in-place on a substrate,the fully cured inventive polyurethane composition exhibits a surfacehardness, which can be termed “impact resistance,” that is surprisingfor a polyurethane coating that also exhibits strong adhesion tosubstrates. Indeed, the cured-in-place polyurethane coatings provide asurprising amount of structural strength to a variety of usefulmaterials, as shown in the Examples hereinafter.

In a further aspect, the invention comprises useful materials derivedfrom the inventive polyurethane compositions. In this regard, theinventive polyurethane materials exhibit exceptional mechanicalproperties as compared to prior art counterparts. For example, whetherused as a coating on a substrate or to generate useful materials, thecured polyurethane composition exhibits a high degree of Shore Dhardness, abrasion resistance, and impact resistance. The inventiveadhesive polyurethane compositions also exhibit a significant degree ofscrew and nail retention, thereby making them desirable for use inconstruction and building applications, as discussed further herein. Thethermal behavior of the inventive polyurethane compositions isexcellent, at least because of the presence of aromatic functionalitytherein.

Still further, the polyurethane compositions are paintable or tintable.The compositions also can be texturized, embossed or the like. As such,the inventive compositions can impart decorative effects to buildingsurfaces coated therewith.

Additives that can be added to the inventive aromatic polyesterpolyether polyol after the substantial completion of the PETtransesterification step but before the addition of isocyanate togenerate the polyurethane can include, but are not limited to, chainterminators, inert diluents, amines, anti-foaming agents, air releasingagents, wetting agents, surface modifiers, waxes, inert inorganicfillers, molecular sieves, reactive inorganic fillers, non-reactivefillers (e.g., flyash, mica, pigments, wood particles), chopped glass,glass fibers, steel wool, steel shavings, processing additives,surface-active agents, adhesion promoters, anti-oxidants, dyes,pigments, ultraviolet light stabilizers, thixotropic agents, anti-agingagents, lubricants, coupling agents, solvents, rheology promoters,anti-oxidants, anti-UV agents, colorants, and combinations thereof.Additives may be utilized in amounts that can be determined by one ofordinary skill in the art according to formulation principles associatedwith the coatings and foams herein.

As noted, polyurethane materials of the invention herein can beformulated with materials derived, at least in part, from renewableand/or recyclable/sustainable content. In this regard, “renewable” or“sustainable” refers to matter that is provided by natural processes orsources. The total recycled and/or renewable/sustainable content of thepolyurethane component (based on the polyols and isocyanates, which insome implementations, may include filler materials) can be greater thanabout 5%, or about 10%, or about 15%, or about 20%, or about 25%, orabout 30%, or about 35%, or about 40%, or about 45%, or about 50% basedon the total weight of polyurethane composition on a weight % basis.Such renewable/sustainable material can be derived from the aromaticpolyester polyether polyol component, glycerin and/or from the use offiller materials. The total recycled and/or renewable/sustainablecontent in the inventive polyurethane can comprise a range that can bedefined by selection of two of the referenced percentages.

Further description of the polyurethane materials, implementations, andapplications are described in detail hereinafter.

The polyurethane composition is the reaction product between theinventive aromatic polyester polyether polyol and an isocyanatecomponent. Significantly, upon mixing of the two components, optionallyin the presence of additional materials, the polyurethane composition iscured-in-place on a substrate to generate a strong adhesion to a varietyof material types, as set out herein. The resulting polyurethanecomposition can be unfoamed or foamed upon application to the substrate.When unfoamed, the composition comprises the inventive aromaticpolyester polyether polyol, a catalyst incorporated into the polyol, andan isocyanate. When foamed, the composition further can comprise anadded blowing agent. Alternatively, foam can be generated throughapplication mechanics, such as by mixing to incorporate air or waterfrom a nozzle or the like.

The catalyst used to accelerate the reaction between the polyol and theisocyanate can include an organometallic catalyst, an amine catalyst, ora combination thereof. An organometallic catalyst, for example, caninclude dibutyltin dilaurate, a lithium carboxylate, tetrabutyltitanate, a bismuth carboxylate, or any combination thereof.

The amount of inventive polyol to isocyanate can vary according to theamount of hydroxyl functionality available to react with the isocyanatemoieties. In regards to the inventive aromatic polyester polyetherpolyols, higher ethoxylation levels on the trimethylolpropane and theglycerin can result in a lower amount of hydroxyl functionality. Itshould be appreciated that the measured hydroxyl functionality in agiven inventive polyol material may be indicative of both PET-containinghydroxyl moieties, as well as any hydroxyl moieties contributed by othermaterials, such as ethylene glycol generated in the transesterificationreaction that was not removed, for example. For the 5 moles ofethoxylation example, the amount of aromatic polyester polyether polyolto isocyanate can be from about 1:1 or about 0.95:1 or about 1:0.95 on avolume:volume ratio of reactive moieties in each component. The amountof materials as a function of hydroxyl functionality and isocyanatefunctionality can readily be determined by one of skill in the art. Aswould be recognized, additives that can be added to either the polyol orisocyanate can result in a variation of the volume ratios to generatethe appropriate reaction ratios, and such variations can be determinedby one of ordinary skill in the art.

The polyurethane composition can be prepared by either the “one-shot” orthe “prepolymer” approach. In the former, all ingredients are mixedsimultaneously, along with catalysts, foaming agents, fillers,plasticizer, and cured-in-place on the substrate or, for the buildingmaterials, in a mold, sprayed via a dynamic mixer, on a pultrusion line,etc. Such systems are generally of two components, consisting of an Acomponent, being the di- or polyisocyanate, and a B component, being thepolyol(s) with any other desired active hydrogen material, catalyst(s)and any other ingredients. In the prepolymer approach, anisocyanate-terminated prepolymer is first prepared by reacting excessdiisocyanate with a polyol. The curing involves the reaction of theprepolymer (A component) with a chain extender (B component), which willcomprise the aromatic polyester polyether polyol of the invention. Theprepolymer approach can be useful when the polyurethane composition isbeing generated in the field or on a job site, as this method canprovide a more controlled reaction/curing process, for example.

As indicated, a significant feature of the present invention is thestrong adhesion generated between the inventive polyurethane compositionand a variety of substrates. Indeed, the present invention exhibitspreviously unseen utility in an industry in which adhesives havegenerally been formulated with specific end uses in mind, as opposed toa “universal” or “multi-functional” adhesive being available. In thisregard, and as discussed previously, the cured-in-place adhesive bondwill be stronger than the internal strength of the substrate to which itis applied for substrates like OSB, FRP, gypsum drywall, as well asother materials. The exceptional adhesive strength of the inventivepolyurethanes shows wide utility for a number of substrate materials asdiscussed further herein.

Without being bound by theory, the inventors herein believe that theexceptional adhesion exhibited by the inventive polyurethane compositionis, at least in part, conferred by the use of terephthalate segmentedpolyols derived from the PET transesterification from use of glycerinand/or trimethylolpropane have the degree of ethoxylation set outpreviously, namely 1 to 9, or any amount of within this range, moles ofethoxylation. Adhesion would be appreciated to be, at least in part, afunction of surface energy. In the present invention, and without beingbound by theory, enhancement of surface energy is believed to begenerated, at least in part, by ether linkages as provided by ethyleneoxide adducts imparted by the ethoxylation of glycerin ortrimethylolpropane. Adhesion can also be influenced by the polarity ofthe molecule, which can also be provided by the PET-derived polyols, asdiscussed above. Moreover, the aromatic character of the polyesterpolyols is also believed to impart at least some additionalhydrophobicity in the polyester polyols, thus conferring bothhydrophobic and hydrophilic character to the resulting polyol. Theinventors hypothesize that such dual functionality can enhance themiscibility of the inventive aromatic polyester polyether polyol in theisocyanate component, and may positively influence the adhesivecharacteristics of the resulting polyurethane composition. Such adhesionis believed to be further augmented by the curing in place, or “in situ”polymerization, feature of the present invention.

When a foamed polyurethane composition is desired, blowing agents areused, as would be appreciated. In certain aspects, the inventivearomatic polyester polyether polyol comprises one or more blowing agentsincluding, but not limited to, physical blowing agents, chemical blowingagents, or combinations thereof. In some aspects, the term “chemicalblowing agents” means compounds that form gaseous products via reactionwith isocyanate, an example being water or formic acid. The term“physical blowing agents” means compounds which have been dispersed,dissolved, or otherwise distributed in either or both of the aromaticpolyester polyether polyol or isocyanate starting material and whichgenerate gas under the conditions of the polyurethane formation herein.In other aspects, the inventive aromatic polyester polyether polyols mayalso comprise one or more blowing agents. Yet further, the blowing agentmay include either or both of a physical blowing agent or a chemicalblowing agent. The blowing agent is selected to substantially notchemically react with the inventive aromatic polyester polyether polyoland/or the isocyanate component independently until the foam productionis desired.

In one implementation, hollow microbeads comprising a physical blowingagent added alone or in combination with other blowing agents to thereaction ingredients for the foam coating. Such hollow microbeads aretypically comprised of a shell made of thermoplastic polymer, with, inthe core, a liquid, low-boiling-point substance based on alkanes, forexample, isopentane. The production of these hollow microbeads isdescribed by way of example in U.S. Pat. No. 3,615,972, the disclosureof which is incorporated herein in its entirety by this reference.Examples of suitable hollow microbeads are obtainable with trademarkExpancel® from Akzo Nobel. When used, the amount added of the hollowmicrobeads is generally from about 0.25% to 5.0%, or from about 1.0% to2.0%. As a non-limiting example, an aromatic polyester polyether polyolof about 24 pcf density can use about 1% by weight hollow microbeads ona weight percent basis of the total polyol:isocyanate mixture. Anexemplary Expancel product is 031 DU 40.

The blowing agent can, independently, be added to either or both of thearomatic polyester polyether polyol or the isocyanate component. In someaspects, when hollow microbeads are used as a physical blowing agent theinventors herein have determined that it can be advantageous to add themicrobeads to the isocyanate component, at least because the microbeadcoating may be partially soluble in the aromatic polyester polyetherpolyol, thus reducing the stability—and resulting foam coatingcharactenstics—of the polyol component. Additionally, heating of thearomatic polyester polyether polyol, as discussed further herein, so asto facilitate flowability can approach the melting point of the coatingwhich, again, would affect the pre-reacted aromatic polyester polyetherpolyol, as well as the resulting foam coating properties.

In further implementations, the blowing agent can comprise a gaseousphysical blowing agent utilized in an amount of from about 1 to about20, about 1 to about 15, about 5 to about 15, about 5 to about 10, orabout 8 to about 10, parts by weight, each based on 100 parts by weightof either or both of the component in which the blowing agent isincorporated within. Such gaseous physical blowing agents can compriseone or more of volatile non-halogenated C2-C7 hydrocarbons such asalkanes, alkenes, cycloalkanes having up to 6 carbon atoms, dialkylether, cycloalkylene ethers and ketones, and hydrofluorocarbons, C1-C4hydrofluorocarbons, volatile non-halogenated hydrocarbon such as linearor branched alkanes such as butane, isobutane, 2,3-dimethylbutane, n-and isopentanes, n- and isohexanes, n- and isoheptanes, n- andisooctanes, n- and isononanes, n- and isodecanes, n- and isoundecanes,and n- and isodedecanes, alkenes such as 1-pentene, 2-methylbutene,3-methylbutene, and 1-hexene, cycloalkanes such as cyclobutane,cyclopentane, and cyclohexane, linear and/or cyclic ethers such asdimethyl ether, diethyl ether, methyl ethyl ether, vinyl methyl ether,vinyl ethyl ether, divinyl ether, tetrahydrofuran and furan, ketonessuch as acetone, methyl ethyl ketone and cyclopentanone, isomersthereof, hydrofluorocarbons such as difluoromethane (HFC-32),1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,2,2-tetrafluoroethane(HFC-134), 1,1-difluoroethane (HFC-152a), 1,2-difluoroethane (HFC-142),trifluoromethane, heptafluoropropane (R-227a), hexafluoropropane(R-136), 1,1,1-trifluoroethane, 1,1,2-trifluoroethane, fluoroethane(R-161), 1,1,1,2,2-pentafluoropropane, pentafluoropropylene (R-2125a),1,1,1,3-tetrafluoropropane, tetrafluoropropylene (R-2134a),difluoropropylene (R-2152b), 1,1,2,3,3-pentafluoropropane,1,1,1,3,3-pentafluoro-n-butane, and 1,1,1,3,3-pentafluoropentane(HFC-245fa), isomers thereof, 1,1,1,2-tetrafluoroethane (HFC-134a),isomers thereof, and combinations thereof. In various aspects, theblowing agent comprises 1,1,1,3,3-pentafluoropentane (245fa), water, ora combination thereof.

If water comprises the blowing agent, water can be utilized in an amountof from about 0.1 to about 5, about 0.1 to about 4, or about 0.1 toabout 3, parts by weight, each based on 100 parts by weight of thecomponent in which the water is included. It is also contemplated thatboth a non-water blowing agent and water may be present simultaneouslyin one or more of the above amounts. Typically, the amount of theblowing agent and/or water is selected based on a desired density of thefoamed polyurethane compositions and the solubility of the blowing agentin the reactive components.

Optionally, in one aspect, a minor amount of a surfactant can beutilized to stabilize the polyurethane reaction mixture until it cures.Such surfactants can comprise a liquid or solid organosiliconesurfactant. Other surfactants include, but are not limited to,polyethylene glycol ethers of long-chain alcohols, tertiary amine oralkanolamine salts of long-chain alkyl acid sulfate esters, alkylsulfonic esters and alkyl arylsulfonic acids. Such surfactants can beemployed in amounts sufficient to stabilize the foaming reaction mixtureagainst collapse and the formation of large, uneven cells. In oneimplementation, about 0.2 to about 5 parts of the surfactant per 100parts by weight aromatic polyester polyether polyols can be sufficientfor this purpose. Such surfactants can enhance the wettability of theapplied mixture to, in some implementations, improve adhesion of theapplied coating or foam to the substrate.

In various aspects, the coating or foam may also comprise a flameretardant additive. Such additive can be selected from the group ofphosphorous, halogens, and combinations thereof. Examples of thesuitable flame retardant additive include, but are not limited to, redphosphorus, ammonium polyphosphate, tris(2-chloroethyl)phosphate,tris(2-chloropropyl)phosphate, tetrakis(2-chloroethyl)ethylenediphosphate, dimethyl methane phosphonate, dimethylpropanephosphonate,diethyl diethanolaminomethylphosphonate, and combinations thereof. Inanother implementation, the conventional flame retardant additive isselected from the group of tricresyl phosphate,tris(2-chloroethyl)phosphate, tris(2-chloropropyl)phosphate,tris(2,3-dibromopropyl)phosphate, red phosphorous, aluminum oxidehydrate, antimony trioxide, arsenic oxide, ammonium polyphosphate andcalcium sulfate, molybdenum trioxide, ammonium molybdate, ammoniumphosphate, pentabromodiphenyloxide, 2,3-dibromopropanol,hexabromocyclododecane, dibromoethyldibromocyclohexane, expandablegraphite or cyanuric acid derivatives, melamine, and corn starch.Additionally, other flame retardant additives are also contemplated foruse in the present invention including, but not limited to, hydratedaluminum oxide, calcium sulfate, expanded graphite, cyanuric acidderivatives, and combinations thereof.

The flame retardant additive amount is determined, in part, by theflammability properties of the low molecular weight ethoxylated triolused in the transesterification reaction. In this regard,trimethylolpropane can, in some circumstances, exhibit more flammabilitythan for a polyol derived from ethoxylated glycerin. Therefore, theamount of flame retardant additive used can be more than that needed fora glycerin-derived aromatic polyester polyether polyol, which isbelieved to exhibit lesser flammability tendency than for a polyolderived from ethoxylated trimethylolpropane. The amount of flameretardant additive will nonetheless be a function of the specificationsfor the material being generated including the inventive polyurethane,as well as the specifications of the finished structure in which thematerial is being utilized. Generally, the amount of flame retardantadditive used is from about 0.1 to about 10% or about 1% to about 8% orabout 1 to about 5% of the total weight of the polyurethane coating.

In certain aspects, the polyurethane composition can be substantiallyfree of flame retardant additives, yet exhibits flame retardanceappropriate for the intended application. In this regard, polyurethanecoatings and foams will exhibit some degree of flame retardancy byvirtue of their chemical makeup, at least because of the presence ofaromatic groups in the polyurethane composition and, optionally, becausethe use of ethoxylated glycerin as a transesterification agent. When theinventive polyurethane compositions are applied as a coating to asubstrate that is inherently flame retardant, for example gypsum wallboard or concrete, flame retardant additives may not be required, or alesser amount may be indicated.

In further aspects, fillers can be added during the fabrication process.For example, fiberglass chop can be incorporated along with Part A andPart B to generate a polyurethane coating composition that exhibitsenhanced structural strength. Other strength enhancing fillers are alsocontemplated, as discussed hereinafter.

The method of generating the inventive polyurethane comprises the stepsof introducing the inventive aromatic polyester polyether polyol and thereactive isocyanate components via spraying using a mixing head toprovide contact therewith on the substrate onto which the coating orfoam is to be formed on and durably adhered to. Dynamic or static mixingheads can be used in the application. Impinging mixing heads can also beused. In various aspects, the application steps are facilitated throughuse of a spray form proportioner device, such as a Graco® Reactor H-VRVariable Ratio Hydraulic Proportioner. Other devices that can suitablybe used include the Nitrosys SPF low pressure sprayer. A KornylakDispensing apparatus can also be used.

To make a rigid polyurethane foam, a mixture generated from a dynamicmixing process can be prepared of a polyfunctional isocyanate, a polyol,a blowing agent, a catalyst, and, optionally, a cell-size regulator(e.g., a surfactant). A urethane-forming reaction begins once theingredients are combined, an exotherm forms, and the blowing agent oragents cause closed cells to form in the polymer as the mass expands andsolidifies. The exotherm typically reaches a peak temperature of atleast about 150° F. The isocyanate and polyol reactants include enoughmolecules with three or more functional groups that the degree ofcross-linking or branching is sufficient to produce a rigid foam.

Although rigid, the polyurethane foams of the present invention also canexhibit resiliency and flexibility, especially at ethoxylation levels offrom about 5 to about 7 moles. The polyurethane foams also exhibitexceptional adhesion. For example, the foams have shown a tendency toadhere to a new Teflon® surface. In this regard, it may be beneficial touse a sacrificial coating when preparing the inventive foams in a moldetc.

The polyurethane can be applied at a point of manufacture (e.g.,products to be sold with such coating at point of sale), or the coatingcan be applied a location (e.g., sprayed in place insulation or adhesivelayers applied at a building site).

For some applications, such as coating of irregular surfaces, thecomponents can be sprayed on the surface and be allowed to cure aftergreen strength is achieved. A continuous process can be also usedwherein the components are dispensed onto a continuous belt. The desiredlength of material can then be generated, and when green strength isacquired, the lengths can be moved to a curing station (e.g., racks) andallowed to cure for about 24 hours. Other application methods can besuitably used.

High or low pressures can be used to generate the polyurethane coatings.Pressure ranges can be from about 500 psi up to about 5000 psi, or fromabout 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, or 5000 psi, whereany value can form an upper or lower endpoint, as appropriate. Thespecific psi value(s) for application can be determined by one ofordinary skill in the art without undue experimentation. Foam coatingsare typically applied at lower pressures than film coatings.

In some implementations, each of the inventive polyester polyol and theisocyanate can be pre-heated so that the individual components and thecombined components are applied at a temperature that facilitates bothflowability and reaction thereof. In this regard, each component can beindependently heated to from about 35 to about 95° C., about 45 to about85° C., or about 50 to about 80° C. or up to about 90° C. Such heatingmay be used to reduce the viscosity of the materials and/or toaccelerate the polymerization reaction and subsequent curing. In someaspects, the inventive aromatic polyester polyether polyols andisocyanate components can have the same or different applicationtemperatures. The pre-heating can be provided in or proximate to eitheror both the storage tanks or application device.

In some aspects, when generating a foam coating or foamed substrateusing a blowing agent comprising gas-filled micro-spheres, it can beadvantageous to combine the aromatic polyester polyether polyol and theisocyanate at temperatures less than the expansion temperature of theblowing agent. Without being bound by theory, the inventors hypothesizethat by allowing the aromatic polyester polyether polyol and theisocyanate to combine at this lower temperature, the curing reactionbetween the aromatic polyester polyether polyol and the isocyanate canat least partially commence prior to the activation of the microspheres.It is believed that such initial curing can, in some aspects, enhancethe resulting adhesion of the foam coating to a representative buildingsubstrate. Moreover, screw and nail retention improvements are observed(e.g., the punctured foam appears to be “self-healing”), possiblybecause of at least some gelation of the aromatic polyester polyetherpolyol and isocyanate components prior to expansion of the blowingagent. To this end, photomicrographs of the adhered foams illustratelocally oriented polyurethane foam layers surrounding the expandedmicrospheres. FIG. 1 is a photomicrograph of an inventive foamedcomposition 100 having expanded microsphere 105 embedded in polyurethane110.

Because a polyurethane curing reaction is moderately exothermic, theheat of reaction will begin to increase, with the temperature risereaching the expansion temperature for the microspheres. The temperatureof expansion is a known quantity for the microspheres. Accordingly, in amethod of making an in situ foamed coating on a building substrate, theinvention comprises selecting a blowing agent comprising hollowgas-filled microspheres, wherein the hollow microspheres have anexpansion temperature. The blowing agent can be incorporated in eitheror both of the aromatic polyester polyether polyol or isocyanatecomponents, wherein the component in which the blowing agent isincorporated is maintained at a temperature of less than the expansiontemperature of the blowing agent. In this regard, if the blowing agenthas an expansion temperature of about 85° C., the component in which theblowing agent is incorporated, for example the isocyanate, will bemaintained at about 5, 10, 15, 20, 25, or 30° C. below this expansiontemperature, or about 80, 75, 70, 75, 70, 65, 60 or 55° C. The othercomponent can be maintained at the same temperature or it can bedifferent, as long as the combined aromatic polyester polyether polyoland isocyanate components are able to react partially prior to expansionof the blowing agent.

Using the expandable microsphere blowing agent as an example, theaddition of a blowing agent at about 1% on a polyurethane compositionweight:weight basis, the density of the coating adhered to thesubstrate, now in the form of a foam can be about the 26-28 pounds percubic foot. At about 1.2% blowing agent the resulting density of thefoam coating is from about 20 to about 26 pounds per cubic foot. Whenusing the expandable microspheres as a blowing agent, the density of thefoam coating can be from about 2 to about 50 pounds per cubic foot.Still further, the density of foam adhered to a building substrate canbe about 2, 5, 10, 15, 20, 25, 30, 35, 40, 45 or 50 pounds per cubicfoot, where any value can form an upper or a lower endpoint, asappropriate.

For polyurethane foams described herein, density ranges of about 0.5 to10 pounds per cubic foot densities can be good for insulationproperties, as shown in the Examples hereinafter. However, the rangecannot be determined by looking at one property alone. For instance, afoam having a density of about 16 to 36 pound per cubic foot can havegood insulation values while at the same time provide additionalstrength and desirable nail or screw retention over lower density foams.For adhesive polyurethanes, a denser, stronger foam in the range ofabout 24 to 60 pounds per cubic foot or even completely unblown materialat about 70 pounds pcf can be used. Sound abatement can be improved whenthe density of the foam itself varies within the layer or layers appliedsuch as a higher density (from about 10 to about 70 pcf) changing to alower density (about 0.5 about 10 pcf) and the back up to higher density(from about 10 to about 70 pcf), embedding the weaker low density foambetween two highly structured, dense, and adhesive outer layers. In thismethod, the average density of the layer might be considered low eventhough within the layer are much higher density areas.

One or more additional fillers can be used in the polyurethane materialsof the present invention. As discussed hereinafter, for variousimplementations, the polyurethane compositions can incorporatefiberglass or other types of binding fibers or carbon particles orfibers, where such fillers can be selected to generate desirable endproperties. Fillers can also reduce the amount of material needed in aparticular application. Examples of such bulking fillers useful ash suchas those produced by firing fuels including industrial gases, petroleumcoke, petroleum products, municipal solid waste, paper sludge, wood,sawdust, refuse derived fuels, recycled materials, switchgrass or otherbiomass material. The one of more additional fillers can also includeground/recycled glass (e.g., window or bottle glass); milled glass;glass spheres; glass flakes; activated carbon; calcium carbonate;aluminum trihydrate (ATH); silica; sand; ground sand; silica fume; slatedust; crusher fines; red mud; amorphous carbon (e.g., carbon black);clays (e.g., kaolin); mica; talc; wollastonite; alumina; feldspar;aroganite, bentonite; quartz; garnet; saponite; beidellite; granite;calcium oxide; calcium hydroxide; antimony trioxide; barium sulfate;magnesium oxide; titanium dioxide; zinc carbonate; zinc oxide; nephelinesyenite; perlite; diatomite; pyrophillite; flue gas desulfurization(FGD) material; soda ash; trona; inorganic fibers; soy meal; pulverizedfoam; and mixtures thereof.

The amount of filler material used, will be dependent, at least in part,on the intended end uses of the compositions and products using thecompositions. The inclusion of fillers in polyurethane materials of thepresent invention can modify and/or improve the properties of thematerials generated from use of the inventive polyurethane compositions.In particular, high filler loading levels can be used in the structuralfoam materials described in detail hereinafter without a substantialreduction of (and potentially with an improvement in) the intrinsicstructural, physical, and mechanical properties thereof. In other words,the materials can be used in applications where load-bearing propertiesare desirable.

Whether foamed or unfoamed, the surface of the inventive polyurethanecompositions are paintable upon completion of curing. The polyurethanecompositions can also be tinted with pigments to provide a coloredpolyurethane material upon completion of curing.

When the coating is foamed, decorative features can be added to give theouter foam surface a “faux look.” In this regard, a wood grain surfacecan be generated. Yet further, a stucco-like surface can be generated.Still further, a textured surface can be generated. Prior to completionof curing, patterns, such as those associated with brick or masonry lookcan be embossed into the surface. When combined with the paintability ortintability of the inventive compositions, the usability of the coatedsubstrates in interior or exterior construction applications wheredesign is a point of materials selection can be enhanced. Perforationscan also be incorporated into the foamed coating, so as to increase theacoustical characteristics of the substrate.

Low/No VOC Substitutes for Polyester Resin Systems and AdhesiveApplications

Currently, polyester resins are widely used as adhesives, both filledand unfilled, in construction and in vehicle manufacture (e.g.,automobiles, motor homes, tractor trailers, etc.), among other uses.Unsaturated polyester and vinyl ester resins comprising these materialstraditionally have been wholly derived from petrochemicals and containhigh concentrations of styrene, a hazardous air pollutant, and a primarycause of VOCs in locations where such materials are used inmanufacturing.

The polyurethane materials of the present invention not only provideexcellent adhesive performance in a variety of use cases that iscomparable to or better than many polyester resins, these materials arestyrene-free. Resins presented herein are also partially derived frombiologically renewable resources and recycled materials, surprisinglywithout showing a decrease in performance. In this regard, the presentinvention provides adhesive systems that are styrene-free and that arelow in VOCs. Significantly, the inventive resin systems are at leastpartially derived from recycled sources and, when ethoxylated glycerinis used, the resins have a sustainable component. Recyclable orsustainable fillers can also be used. Thus, the inventive materials aresignificantly more “green” than possible with previous resin systemswhere strong adhesion to a variety of surfaces is desired.

The inventive adhesive systems can be used to replace styrene-containingpolyester resins that are used to generate composite systems. Theinventors herein have surprisingly found that the polyurethanes of thepresent invention can wet out fiberglass and other filler materialsquickly and efficiently. In one example of such an application, thepolyurethanes of the present invention can be used to prepare laminatedpanels for motor homes, recreational vehicles, and trailers, asdisclosed in U.S. Provisional Patent Application No. 62/722,874,previously incorporated by reference. To briefly summarize thatapplication, a gel coat can be applied to a belt or a mold and theinventive polyol and isocyanate are mixed by spraying in the presence ofchopped fiberglass, and allowed to cure to generate a strong,lightweight composite sheet material that is resistant to waterinfiltration and cracking. When combined with the substantialelimination of VOC generation in manufacturing, the invention describedin the referenced application is a significant improvement over themethodologies used today. While this specific application uses afiberglass filler material, other fillers are contemplated to generatecomposite sheet materials can be using this technique.

In a further implementation, the present invention can be used toprepare structurally-strong molded materials that are filledappropriately for the desired use case. For example, fiberglass fillerscan be used to generate composite structures that are suitable for usein vehicles, such as for the molded portions of recreational vehicles,boat hulls, shower stalls, bathtubs, pool shells, among other things.Carbon fibers can be used to generate lightweight and strong compositestructures for aircraft parts. Still further, other fillers can be usedas discussed elsewhere herein.

Yet further, the filled polyurethanes can be formed as sheets, with adecorative outer layer, or both layers can be decorative. Such materialscan be used as walls for vehicles such as motor homes, trailers, andrail cars, among other things. In some implementations, a vehiclecomprising such sheet materials provide insulative characteristics.

Still further, the inventive aromatic polyester polyether polyols can beused as components in epoxy adhesives. The aromatic polyester polyetherpolyols can be used as precursors for acrylate-based adhesives.

Substrates Coated with Inventive Polyurethane Compositions

In broad constructs, the present invention relates to substrates havingthe inventive polyurethane composition material adhered to one or moresurfaces thereof, wherein the polyurethane composition is in either anunfoamed or foamed configuration, as discussed in detail herein. Thestrong adhesion to a variety of surfaces including, but not limited, tobuilding and construction-related surfaces, as well as the one or moreexcellent physical properties exhibited by the cured-in-place foamed orunfoamed implementations can allow the inventive polyurethanecompositions operate effectively as a nearly universal adhesivematerial. While some exemplary configurations of the specific compositesubstrates are discussed further hereinafter, generally, the substratecoated with the inventive compositions can comprise any material. Innon-limiting examples, the inventive compositions can be adhered to wallmaterial, roofing material, flooring material, gypsum wallboard, OSBboard stock, plywood, lumber, cement cladding/siding, rigid foam,flooring material, extruded polystyrene, expanded polystyrene, concrete,wood planking, steel, aluminum, polyiso insulation, fiberglass, HDPE,MDPE, LDPE, fabric, paper, paperboard, MDF, plastic, cellulosematerials, among other things. The inventive polyurethane compositionsherein are contemplated to provide enhanced physical properties whencured-in-place on each of the substrates.

In this regard, the composite substrates of the present inventioncomprise the polyurethane coating that is generated via in situpolymerization of the inventive aromatic polyester polyether polyols anda suitable urethane-containing reactant on a surface of the substrate.The polyurethane coating in the form of a film or a foam is durablyattached to one or more surfaces of the substrate substantially by theexceptional adhesive properties of the polyurethane composition, and notby use of any secondary adhesive or tie layer.

The polyurethane coating can be applied to one or both sides of asubstrate, thereby providing a substrate having the inventivepolyurethane material adhered thereon. Yet further, the inventivepolyurethane coating can be included as an internal sandwich layerbetween two substrates, wherein the interior side of each substrate isadhered to the polyurethane coating. The adhered substrates can be thesame or different in such a sandwich structure.

The method of generating the layered or foam coated substrates cancomprise the step of spraying or using a dynamic mixer the inventivearomatic polyester polyether polyol comprising the catalyst component,along with any other ingredients as discussed hereinafter, and theisocyanate onto the substrate to generate in situ formation of the rigidfoam to be firmly adhered to the substrate surface thereof. In oneaspect, the pre-heated isocyanate (Part A) and polyol/catalyst mixture(Part B) can be applied to the substrate via a spray gun or dynamicmixing head as discussed elsewhere herein. In other aspects, the methodfurther comprises the step of combining inventive aromatic polyesterpolyether polyol with catalyst, the isocyanate component to form amixture.

In one implementation, the mixture can be applied to the substratesurface in a single application. In a further aspect, the mixture can beapplied in two applications, whereby this implementation incorporates afirst application to the surface as a light base coating, allowed tocure for about 1 or 5 or 10 minutes, and then a second application isprovided as a complete application. The first application can enhanceadhesion of the layer or coating to the substrate surface.

Overall, the coatings are generally about 80% or about 90% or about 95%cured within about 1 or 2 or about 6 hours to generate “green strength,”and will be totally cured in about 12, 24 or 36 hours or up to about oneweek when the composite material is maintained at conditions from about50° F. to about 110° F.

Fire Resistant Building and Other Materials

The compositions and methods of the present invention can be used togenerate fire resistant coatings for various building materials.Currently, building materials, such as OSB, I-joists etc. can besupplied with all surfaces (e.g., encapsulation) or partially coatedwith magnesium oxide. An example of such treatment is shown in US PatentPublication No. US2015/0052838, the disclosure of which is incorporatedherein in its entirety. While magnesium oxide is non-combustible,problems can arise with its use. For example, the coating can befriable, thus exposing the surface, and reducing the fire resistancecharacteristics. It is not useable under conditions of high relativehumidity and in high salt conditions.

In contrast, when applied to a building substrate, the coatings of thepresent invention are substantially not friable. Rather, they areresilient and at least partially self-healing, as shown at least by thescrew retention and Cobb Ring results hereinafter. Moreover, thesematerials are fire retardant by the nature of thermoset polyurethanefoams generally, as well in relation to the additional benefits believedto be conferred by the presence of aromatic groups in the inventivearomatic polyester polyether polyols.

To this end, the polyurethanes of the present invention are thermosetfoams that can exhibit markedly different fire behavior than seen withpolystyrene foams and other thermoplastic foams. Polyurethane thermosetfoams do not melt at high temperatures. Instead, they form a stable charthat can substantially prevent flame spread and can generate somethermal protection to the surrounding foam, thus increasing the overallservice temperature of the foams. Moreover, because the foam does notmelt, voids are not created, fire can be less likely to spread withinthe panel. Thermoset polyurethane foams also tend to have slightlyhigher ignition temperatures than thermoplastic foams; consequently,they have slightly longer flame spread times. Service temperaturesgreater than the about 90° C. for expanded or extruded polystyrene arealso possible with the materials of the present invention. The aromaticcharacter of the inventive polyurethane foams provide improvements overthe basic properties shown by thermoset polyurethane coatings generally.

The foamed polyurethane materials of the present invention can also beused to store materials or items that are prone to causing fires. Inthis regard, boxes or containers can be generated in which lithium ionbatteries can be better stored for use in vehicles, etc. The strongstructural characteristics of the inventive materials can help protectthe battery from puncturing, etc., but if the battery fails, fire damagecan be reduced due to the fire resistant properties of the materialsherein when prepared into a structural foam material.

Additionally, the inventors believe that the use of glycerin as atransesterification material can further improve the fire resistance ofthe inventive polyurethanes. That is, the chemical structure of theglycerin in its neat form does not readily lend itself to ignition.Thus, when included in the polyurethane backbone, such lack of ignitionappears to translate to a higher heat resistance than expected. Whileflame retardant additives could still need to be added to the materialto comply with certain fire and building codes, it is expected that thefire resistance behavior of the polyurethanes made with glycerin couldbe enhanced.

Construction-Related Definitions

The term “R-value,” as used herein, refers to the measure of thermalresistance as is routinely used in construction industries. The R-valueis the ratio of the temperature difference across the insulator to theheat flux through the insulator. In the United States, R-values aretypically given with the units of ft²·°·Fhr/Btu. R-values are routinelyreported without units and, as used herein, unless the units areotherwise indicated the R-values are reported in U.S. units of ft²·°F.·hr/Btu.

Gypsum wallboard (also called “drywall” or “sheetrock”) is a buildingmaterial comprising a core comprising set gypsum sandwiched between twosheets of multi-ply paper facing material for use in the construction ofresidential homes, commercial buildings, and other structures. The useof paper-faced gypsum wallboard is one of the most common means offinishing the interior structure of buildings. Gypsum wallboard alsoconfers fire-resistance. Paper-faced gypsum wallboard, also known as“sheetrock” or “drywall” is usually manufactured (pre-cut) in flatsheets of 4 ft. by 8 ft., or 4 ft. by 12 ft., typically having athickness of ½ inch or ⅝ inch or as otherwise available for use. Aswould be recognized, the panels of the paper-faced gypsum wallboard arehung on wood or metal studs to form the interior partitions or walls ofrooms, elevator shafts, stairwells, ceilings and the like.

Oriented strand board (“OSB”) is a type of engineered lumber similar toparticle board, formed by adding adhesive to wood strands/flakesarranged in specific orientations followed by application ofcompression. Adjustments to the manufacturing process, such as in theorientation of the wood fibers/flakes can impart differences inthickness, panel size, strength, and rigidity. OSB panels have nointernal gaps or voids, and are water-resistant, although they dorequire additional membranes (i.e., “housewrap”) to generateimpermeability to water. The finished product has properties similar toplywood, but is uniform and less expensive. OSB is a material withfavorable mechanical properties that make it particularly suitable forload-bearing applications in construction. The most common uses are assheathing in walls, flooring, and roof decking, although other uses arecontemplated.

Plywood is a sheet material manufactured from thin layers or “plies” ofwood veneer that are glued together with adjacent layers having theirwood grain rotated up to 90 degrees to one another.

Panelized construction or “panelization” is the process of building amodular wall, roof and floor sections in an environmentally controlledmanufacturing facility and delivering them to the construction site forinstallation. These panels are oftentimes referred to as “structuralinsulated panels” (“SIPs”).” In this regard, SIPs are components in highperformance building systems used in residential and light commercialconstruction. The panels consist of an insulating foam core sandwichedbetween two facings. The facing is conventionally oriented strand board(OSB), but can also comprise plywood as a substitute for OSB or, in somespecialized applications, steel or aluminum. SIPs have utility, forexample, in panelized construction, where prefabricated buildingcomponents are assembled into larger panels before being shipped to abuilding site. When wall, floor and roof components are pre-assembled ina climate-controlled environment, builders and developers can save timeand money with improved speed and ensured quality. Fabricationcapabilities vary, but firms that target commercial construction cantypically fabricate wall panels up to about 60 feet long (or more) andup to about 16 feet tall. Roof and floor systems can also be panelizedin similar-sized sections using dimension lumber, trusses or I-joists.SIPs are an element of modern panelized construction. SIPS have alsobegun to emerge as a viable alternative to stick framing walls on thejob site, or even producing stick framed walls at some off-sitelocation. They can reduce onsite labor requirements and the amount ofmaterial needed, while improving the energy efficiency of the wallassembly. They can fabricate simply (i.e., cutting openings for doors,windows), ship flat, and assemble in a comparatively simple manner usingtraditional carpentry techniques.

Fiber cement siding is a building material used to cover the exterior ofa building in both commercial and domestic applications. Fiber cement isa composite material made of sand, cement and cellulose fibers. Forresidential household applications, fiber cement siding generally issupplied at about ⅚ or ⅝ inch thick and in varying lengths of from about18 inches by 6 feet to about 4 by 12 feet. For multi-family residentialor commercial buildings, fiber cement can be supplied in various sizesin accordance with architectural specifications.

Laminate flooring is a multi-layer synthetic flooring product fusedtogether with a lamination process. Laminate flooring simulates naturalmaterials, namely wood and stone, with a photographic layer appliedunder a clear protective layer.

Polyiso insulation is a closed-cell, rigid foam board insulationcomprising a lower density foam layer adhered to one or two layers ofhigher density foam.

Cladding generally refers to construction components that are attachedto the primary structure of a building to form non-structural orexternal surfaces to control an internal environment. Although claddingdoes not typically contribute to a structure's stability, it does playan important structural role in transferring wind loads, impact loadsand its own self-weight back to the structural framework.

Extruded polystyrene insulation (“XPS”) is manufactured through anextrusion process. This manufacturing process involves melting togetherthe resin and other ingredients. The liquid formed is then continuouslyextruded through a die and expands during the cooling process. Thisproduces a closed cell rigid insulation. Expanded polystyrene insulation(“EPS”) is manufactured using a mold to contain small foam beads. Heator steam is then applied to the mold, which causes the small beads toexpand and fuse together. This manufacturing process does not form atrue closed cell insulation as there can often be voids between each ofthe beads where they are not touching one another.

Medium density fiberboard (“MDF”) is an engineered wood product made bybreaking down hardwood or softwood residuals into wood fibers, often ina defibrator, combining it with wax and a resin binder, and formingpanels by applying high temperature and pressure. MDF is generallydenser than plywood.

Laminated veneer lumber (“LVL”) is an engineered wood product producedby gluing together layers of wood veneers with the wood grains inparallel lumber. LVL uses wood fragments that are all oriented in thesame direction to produce very stiff beams that generally have greaterspan capacity than sawn lumber. It can be used for laminated wood beams,timbers, I-Joists, and other engineered wood products. Typically, anindividual LVL ply or layer of veneer is about 45 mm to 65 mm inthickness, and may be up to about 1.2 meters wide and as much as about25 meters in length, depending on the size of the original tree.

Fiberglass reinforced panels (“FRP”) are made of inorganic fiberglasswith a thermosetting resin, formed into flexible, semi-rigid or rigidboards of varying densities. In some implementations, FRP is used asinsulation on trucks, vessels, equipment, chillers, hot and coldequipment, heating and air conditioning duct work, acoustical wallpanels, specialized ceiling applications, power and process equipment.When used as an insulation, fiberglass board can be used at operatingtemperatures from about below 0 to about 450° F.

Subflooring is the thick flat surface on which all other flooring layersrest. Subfloor is the bottom-most layer and it rests on joists.Subfloors are typically made of plywood or OSB and ranging in thicknessfrom about 19/32″ to 1⅛″ thick.

Underlayment is positioned between the structural subfloor of a buildingfoundation and the flooring material. Underlayments are meant to absorbthe roughness, or imperfections of subfloors, so that the flooring canbe installed on top of a smooth, hard surface that will give theflooring material extra support.

Paperboard is a thick paper-based material. While there is no rigiddifferentiation between paper and paperboard, paperboard is generallythicker than paper, for example, over 0.010 in, or 10 points). Accordingto ISO standards, paperboard is a paper with a grammage above 224 g/m²,but there are exceptions. Paperboard can be single- or multi-ply.Paperboard can be easily cut and formed, is lightweight, and because itis strong, is used in packaging.

“Moisture resiliency” is an emerging concept in the constructionindustry. With the increasing occurrence of flooding in coastal andother regions, there has been an increased emphasis in making structuresbetter able to handle periodic water infiltration without causingsubstantial damage, thus lowering repair costs associated with flooding.In this regard, storm surge is a rise in sea level that occurs duringtropical cyclones, intense storms also known as typhoons or hurricanes,and tropical storms. The storms produce strong winds that push coastalwaters into shore, which can lead to flooding. This makes for verydangerous conditions for coastal regions. Heavy thunderstorms, orlong-lasting rain events often times generate much rain that saturatesthe earth's surface and the soils in a given low-lying area may not becapable of filtering the rain water fast enough which can result inriver flooding. If either one of these events take place, the floods canwreak destruction on a structure. Along the coastal regions, many homesare elevated to a height greater than a potential surge flooding event.In low-lying areas close to rivers or tributaries, many of the homes areconstructed with a basement or crawl-space to give some elevation abovethe floodwaters. Many structures are constructed with masonry orconcrete in anticipation of such an event. However, many of thesestructures are built-out internally with common construction materials,such as gypsum drywall interior walls and hardwood or laminate flooring,which will have to be replaced after such catastrophic storm events. Theinteriors of structures are increasingly vulnerable to recurring damagefrom water infiltration. When a structure, or the materials used in theconstruction or reconstruction thereof are designed to be “moistureresilient,” there is a lesser propensity for irreversible water damageresulting from storm surge, flooding, or the like. As one example,moisture resilient wall and flooring materials will be substantiallyresistant to mold growth after contact with water resulting from a waterinfiltration event.

A “surge wall” is a panelized component that is constructed to, in someimplementations, provide moisture resiliency in a structure, as suchterm is defined herein. A surge wall can be incorporated in a lowerportion of a wall structure, for example, an interior wall, to reducethe propensity of the structure to be subjected to irreversible damagefrom water infiltration, such as apparent in a storm surge or otherflooding scenario. In this regard, the lower portion of a wall cancomprise a water-resilient material, with the upper portion of the wallbeing comprised of conventional building materials, such as gypsumdrywall.

An engineered shear wall board, or a storm board, is a structural panelthat can be used, for example, in areas where wall bracing is indicated,such as in hurricane prone areas. Engineered shear wall boards are usedin structures when wind loads equal or exceed 100 mph. Shear wallsgenerally include hold downs at each segment, and are designed in eachstructure in relation to the projected wind speeds that could occur in aparticular location.

Composite Building Panels

In some aspects, the present disclosure provides lightweight compositebuilding panels thereby making installers jobs easier, less strenuousand safer in overhead ceiling applications, roofing applications, or inother above ground applications. While the description below is directedtoward materials that are specifically used in the building andconstruction industry, it is to be understood that other types of usecases are contemplated herein.

In various implementations, the composite panels can have a weight thatis at least 10% less, 20% less, at least 30% less, at least 40% less, orat least 50% less or even less than the weight of a non-compositepanel—that is one comprising the same building substrate without thepolyurethane coating—having the same overall thickness, where suchoverall lower weight is, significantly, acquired without sacrificingstructural strength. In this regard, the composite panels of the presentinvention are at least substantially equal to the strengthspecifications of an uncoated substrate having the substantially thesame dimensions, with the weight of the coated substrate is at leastabout 10% or 20% or even less in weight.

In various aspects, the composite panel can have an impact resistancethat is greater than the impact resistance of a non-composite panelhaving the same overall thickness and dimensions. In this regard, theimpact resistance of a composite building substrate of the presentinvention is at least about 10% greater, or about 20% greater, or about30% greater, in impact resistance than an uncoated building substrate.

The thermal resistance provided by the composite building substrates ofthe present disclosure can reduce the amount of insulation the required,for example, as used in ceilings, walls, and floors, for example. Insome cases, implementations of the inventions herein may reduce orsubstantially eliminate the need for additional insulation depending onthe thicknesses of the panels. With regard to coated gypsum wallboard,which is discussed in more detail hereinafter, the composite substratesof the present disclosure can, at a nominal thickness of ½ inch, provideimproved thermal resistance values when compared to a standard ½ inchdrywall panel commonly used today, as shown in the Examples hereinafter.When fastened, the screws or nails openings can be “self-healing” so asto make a substantially watertight seal so that water is less likely totravel along the screw or nail surface to permeate into the substrate.

Composite substrates are provided herein where the polyurethane layer isfoamed and comprises substantial portion of the thickness of thecomposite substrates, e.g., the polyurethane layers make up at leastabout 25%, 30%, 40%, 50%, 60%, or more of the thickness of the compositesubstrates. As would be recognized, such thickness increase will resultwhen the polyurethane coating is foamed. The coating can comprise athickness that is at least about 10% of the thickness of the compositebuilding substrates. The coating applied can have a thickness of about ¼inch to about 2 inches, about ½ inches to about 1 inches, or otherthicknesses as may appropriate for the application.

When the coating is unfoamed, that is in the form of a layer, thethickness of the coating can be from 10 mils to about 100 mils or fromabout 30 to about 60 mils in thickness on each of the surfaces of thebuilding substrate. When thicker coatings are desirable, the coatingscan be applied in multiple layers, as would be appreciated.

The polyurethane layers or foams can be applied in-line in themanufacturing process of the building substrate. In the manufacture ofgypsum wallboard, for example, the slurry is baked in an oven. Rightafter the oven that bakes the slurry the gypsum wallboard is still hot.At that point, the residual heat in the wallboard can facilitate thecuring of the polyurethane composition However, as noted previously, itcan be beneficial to keep the aromatic polyester polyether polyol andisocyanate components at a temperature below the expansion temperatureof the blowing agent, if an expandable microsphere blowing agent isused.

If produced in high volume, the polyurethane application and in situpolymerization can be performed in line, either fully continuous orusing a diverting line, and using a dynamic mixing application. Forback-coating applications, a coating, film, or foamed layer the panelscan be rotated face down: carefully preserving the facing side that wasrotated up to keep from marking or roll burning in the oven. Afterwardthe polyurethane components can be applied to the substrates, held inline for a certain curing time, and the processed for shipment and sale.

The composite substrates can also be made in an off-line treatment,i.e., using substrates that have already been produced in conventionalmanufacturing processes. An off-line treatment can take severalapplications. The polyurethane components can be applied to thesubstrate using high pressure impingement or dynamic mixing heads can bedelivered to a first side of the panel or substrate and allowed to curebefore further processing.

The composite panel can be used in a variety of building or constructionapplications. In non-limiting examples, the panels can be used assiding, cladding, composite structural panels, insulation, sub-flooring,underlayment, fire-resistant materials, enhanced gypsum drywallmaterials, flooring, structural components, and others.

Functional properties provided by the coated materials herein caninclude, in non-limiting examples, structural support, air barriers,thermal insulation, water resistance or water proofing, air barriers,acoustic enhancements, sound barriers, fire resistances, decorativecoatings, faux coatings, MDF substitutes, among other things.

In a notable aspect, when used as substrate coatings, the polyurethanesof the present invention can impart moisture resiliency. When used inpanelized construction components, the inventive building substratescoated with the inventive polyurethane compositions or buildingmaterials derived from those compositions can be used to providestructural panels that can withstand a water infiltration event, thusenabling the building owners from needing to remove and replace thematerials from the flood exposed areas, for example. In this regard,when a storm surge or other water infiltration source comes into contactwith a structure in which the coated building substrates and/or buildingmaterials are incorporated, the structure will have a lesser propensityto become saturated with the water for a long enough time period inwhich mold can take hold. The lack of water saturation can translateinto those areas of the structure in which the inventive materials areused being substantially mold-resistant, thus reducing or substantiallyeliminating expected damage from water infiltration.

Composite Gypsum Wallboard Panels

In an implementation, the present invention comprises gypsum wallboardthat is coated on one or both sides with the inventive polyurethanefilms or foams. Yet further, the inventive polyurethane coating can besandwiched between two pieces of gypsum wallboard. In someimplementations, application of the inventive layer or foam coating canimpart strength to the gypsum wallboard over that which is seen withconventional coatings. In this regard, the polyurethane compositions ofthe present invention can allow gypsum wallboard to be light weightedvs. conventional materials. For example, wall and ceiling applicationsrequire a conventional drywall panel to be a minimum of ⅜ inch thick orin many instances thicker to achieve the required strength anddurability necessary for these applications. However, gypsum wallboardof standard dimensions (e.g., 4 ft.*8 ft.) is extremely heavy anddifficult to handle, especially in overhead applications. Thickerdrywall panels used in the art lack impact resistance and can be easilydamaged. The inventors herein have found that coating of thinner gypsumwallboard panel, such as ¼ inch or ⅜ inch with the polyurethanecompositions herein can impart a comparable strength over the uncoatedwallboard having the same dimensions. The coating imparts impactresistance. Moreover, the polyurethane coatings can also impart someinsulative qualities to the gypsum wallboard. Fastenability of thepanels to the building structure is not reduced and, in fact, may beimproved according to the screw retention results discussed elsewhereherein.

The structural strength characteristics of the polyurethane coatedgypsum wallboard can allow lighter weight sheets to be used without theexpected sagging that might result when hanging the wallboard onceilings etc. In this regard, the ½ inch gypsum wallboard can be coatedwith ½ inch of the inventive polyurethane composition at a density of 24pounds to provide a total thickness of 1 inches, but at lower pounds persquare foot than would be present in an inch thick gypsum product 4 footby 8 foot product, if such a material would even be available. Theimproved structural strength would allow a composite gypsum wallboardhaving a lighter overall weight to be hung from joists or rafters spaced24 inch on center, which is becoming more common in energy-efficientconstruction in locations of heavy or sagging insulation, wet ceilings,or high humidity instead of the higher weight ⅝ inch drywall, which isheavier than ½ inch gypsum wallboard coated with ½ inch of the inventivecoating at 24 pounds density.

In one aspect, the coated side of the gypsum wallboard panel can faceinwards towards the wall or ceiling cavity. The coated side of thecomposite gypsum wallboard panel, in some implementations creates amoisture resilient and substantially mold resistant barrier. The moldresistant surface created by the polyurethane coating provides acomposite gypsum wallboard panel for use in applications where humidityand moisture are common such as ceiling or wall cavities found inbasements, attics or other exterior wall in residential, commercial orindustrial applications where drywall is commonly used. The moistureresilient and mold resistant barrier can provide protection in areasthat are conducive for mold growth but cannot be easily monitoredwithout specialized equipment. As noted, the coating can provide someinsulative characteristics to the wallboard in this regard, as well.

Yet further, the wallboard panel can be installed with the polyurethanecomposition coated side facing outward, that is, on a room facing sideso that the coated side is visible. Such application is useful in areaswhere grease and dirt can be a problem, such as kitchens or industrialfacilities. The polyurethane composition is readily washable, as well aspaintable. Further, foamed coating is embossable or texturizable, as setout further herein.

Gypsum drywall coated with the foamed polyurethane compositions of thepresent invention demonstrates superior screw and nail retentionproviding a self-sealing means of fastening over conventional gypsumdrywall. Such screw and nail retention can be beneficial when thedrywall is mounted in locations where vibration maybe a problem, such asin a motorized home or in an industrial facility.

An acoustical panel can reduce the noise in adjacent rooms when comparedto traditional drywall panels. It is well known that foamed structureswith areas of low density (foamed cells) surrounded by areas ofincreased density are useful as sound deadening barriers. Though thereis prior art utilizing a gypsum sandwich panel today, the inventivepolyurethane coating used in the present disclosure can provide improvedstructural integrity with better adhesion and sound dampeningcapabilities than prior art products. In this regard, gypsum drywallsandwich structures having a foamed polyurethane compositiontherebetween have utility for modular wall configurations where sounddeadening capability would be beneficial in combination with structuralstrength, whereby the panels may not need to be anchored to studs.Instead the sandwich panels could be anchored from either or both of theceiling or floor via permanent or semi-permanent fasteners.

OSB Composite Panels

In a further aspect, the present invention comprises OSB panels that arecoated on one or on both sides with the inventive polyurethanecomposition, or as an adhesive coating for a sandwich panel. Such OSBpanels can be used for outer walls, flooring, or roofing, asnon-limiting examples. The polyurethane coating can be in the form of alayer or as a foam coating.

The cured-in-place polyurethane coating material exhibits a strong bondto the OSB surface. To this end, it is surprisingly found that theinventive polyurethane coating did not peel or otherwise lose adhesioneven when the coated OSB board was boiled in water for several minutes.

In some aspects, the inventive polyurethane composition can be used asan internal binder for the OSB fibers themselves. When combined with acoating of the inventive polyurethane material, adhesion to the OSB canbe excellent.

OSB panels are quite heavy. The differing thicknesses will be indicatedby the specific applications, with thicker and heavier boards used inapplications where more structural strength is required. The inventorsherein have found that polyurethane compositions of the presentinvention can allow thinner OSB to be used substantially withoutsacrificing structural strength. This not only allows lighter weightthat is, thinner, OSB panels to be used, but also can reduce materialscost. Yet further, some insulation value is imparted to the OSB. Similarresults are found when plywood sheeting is coated with the polyurethanecomposition of the present invention. Fastenability of the panels to thebuilding structure is not reduced and, in fact, may be improvedaccording to the screw retention results discussed elsewhere herein. Inone aspect, a conventional OSB panel can be coated with the inventivepolyurethane composition to provide an OSB panel having greaterthickness. The resulting coated board will have greater structuralstrength than the original uncoated OSB panel, but will have less weightthan a comparable thickness OSB panel. To illustrate this concept, andas a non-limiting example, addition of an inventive foam coating to a ¼inch OSB panel to generate a coated OSB panel having a thickness of 5/16inches would provide a weight of the resulting OSB panel of less thanabout 1.1 pounds per square foot, even while the structural strength ofthe coated ¼ inch OSB panel would be greater than the structuralstrength of the uncoated OSB panel. As another example, a ½ inch OSBpanel can be coated with a thickness of inventive polyurethane foam toprovide a thickness in the coated OSB panel of ⅝ inch. The weight of the⅝ inch board would be less than about 2.1 psf, even while the structuralstrength of the coated OSB panel would be greater than the ½ inchuncoated OSB panel.

OSB Structural Insulated Panels

Yet further, the polyurethane composition can be foamed and sandwichedbetween two OSB panels to generate a SIP. Such SIPs are useful forbuilding panelized construction elements. Yet further, such panels areuseful for creating modular room configurations, such as is often donein office environments.

While OSB SIPs are known the art, generation of such SIPs using the insitu polyurethane composition of the herein provides, in one aspect, amore efficient manufacturing process. This is due, at least in part, tothe elimination of a separate foam generation step and subsequentadhesion step, as is currently required in the fabrication of OSB SIPs.In one example of this process, one or both of an interior facing sideon two OSB panels can be coated with the polyurethane components on aline. The respectively coated sides can then be brought together shortlyafter application. Each of the coated sides can then meld as part of thecuring process to generate a foamed interior sandwiched between two OSBpanels. The polyurethane foam sandwich layer will be adhered to each ofthe interior sides of the OSB panels as a result of the in situpolymerization process discussed herein. As discussed previously, theunique and surprising strength of the bond between the cured-in-placeinventive polyurethane compositions means that a separate adhesive layeris not needed to ensure adhesion of the foam layer to the OSB panel(s).

Moreover, the impact resistance of OSB boards is a known limitation withconventional SIPs. Indeed, OSB can crack or splinter if there is not aprotective cladding or siding applied on top, such as a siding. The highimpact resistance of the inventive polyurethane SIPs providessubstantial improvements to thereby allow the SIPs to be durably used asexterior surface components.

Adhesives

The present invention can also be used as an adhesive, whether in foamedor an unfoamed condition on a wide variety of substrates including, innon-limiting examples, gypsum wallboard, OSB board stock, plywood,lumber, cement cladding/siding, rigid foam, flooring material, extrudedpolystyrene, expanded polystyrene, concrete, wood planking, steel,aluminum, polyiso insulation, fiberglass, HDPE, MDPE, LDPE, fabric,paper, paperboard, MDF, plastic, cellulose materials, among otherthings. As discussed herein, the polyurethanes of the present inventionhave exceptional adhesion, while at the same time exhibiting propertiessuch as resiliency, impact resistance, etc., where such properties canbe selected for a particular use.

In a specific example of an adhesive utility for the constructioncontext, for example, the polyurethane can be applied on framing,followed by application of a material, such as drywall (if an interioroperation) or a OSB, siding etc. (if an exterior operation). Thematerial can be attached using standard methodology (such as nailing,screwing etc.), however, the addition of the adhesive, especially whenfoamed, can increase the resiliency of the attachment. For example, whenused between a stud and the backside of drywall, the point of attachmentbetween these two building elements can be improved due to the screwretention aspects of the inventive polyurethane material, as discussedelsewhere herein. The exceptional adhesion in the present invention isalso observed with foamed polyurethane layers on a number of surfaces.

Polyurethane Coated Structural Insulation Panels

In further implementations, the polyurethane composition can be used togenerate a new form of SIP. In this regard, a building substrate havingat least some insulative properties, for example, XPS or EPS, forexample, can be coated on both sides with the inventive polyurethanecomposition, wherein the polyurethane composition has at least somefoamed characteristics and is cured-in-place on the panel material.

Still further, the cured-in-place inventive polyurethane composition canbe adhered to only one side of the XPS or EPS foam. In this regard, whenassembled, the inventive SIP will have one surface in which the foamcore is exposed prior to finishing. Such an exposed foam surface may besatisfactory for some applications, such as when the SIPs surface isused as an interior wall surface. In a notable distinction from priorart panels prepared from XPS or EPS, the cured-in-place polyurethanecoating substantially does not result in melting of XPS/EPS due to therelatively low temperature of the exothermic curing reaction. This meansthat instead of requiring a finished layer to be adhered, such as via atie layer, to the outer surface of the EPS panel, the polyurethane layercan be cured-in-place on the surface of the EPS panel. In this regard, afirst layer of a mixture of aromatic polyester polyether polyol andisocyanate (foamed or unfoamed) can be applied to the outer surface ofan EPS panel. That layer can be allowed to cure slightly, and then asecond coating can be applied to provide the desired thickness of thepolyurethane coating. The coated panel can also be polyiso or othertypes of insulating material.

The resulting panel, which can be characterized as a foamed insulativecore sandwiched between inner sides of a cured-in-place polyurethanecomposition, exhibits surprising structural strength while also beinglightweight and highly insulating, as well as providing substantialsound barrier characteristics. In this regard, this inventive SIP can beused in panelized construction, to create modular interiors, insulatedwall panels, etc.

In contrast to conventional structural insulating panels that areconstructed from OSB panels having an about 3 to 8 inch, or about 4 to 6inch piece of foam incorporated within two OSB panels, the inventivestructural insulating panels are very lightweight. OSB clad structuralinsulating panels can weigh from about 90 to about 100 pounds, or fromabout 2.8 to about 3 pounds per square foot. Since the polyurethanefoam-coated panels are much lighter than an equally dimensioned (length,width, height, and thickness) OSB panel, the overall weight of a SIPcomprising two foamed panels having a foam core sandwiched therebetweenis at least about 10% less or at least about 20% less or at least about30% or more less in weight per square foot than an equally dimensionedstructural insulating panels formed from OSB panels having an about 3,or about 4, or about 5 or about 6 inch thick piece of closed cell foamsandwiched therebetween. Each of the inventive polyurethane panels thatform a first and a second structural panel within which the foamed coreis sandwiched can each be from about ¼ inch to about 1 inch or greaterin thickness, or any of the standard thicknesses in which OSB isconventionally provided.

As would be recognized, adhesion between the foam core and the SIP outerlayers is a common point of failure, especially in areas where extremelyhigh or low temperatures are possible, or where large temperaturevariations are common. The excellent adhesive characteristics of theinventive polyurethane compositions can substantially eliminate thisdelamination problem. This improved adhesion is augmented by the uniquecure in place features of the

An example where the one or both sided polyurethane coated XPS or EPScan be used is for acoustical or soundproofing panels, especially whereit might be desirable to reduce sound transmission through walls, whilestill providing a paintable or decorative surface. When used in officeenvironments, the acoustical or soundproofing panels comprising foamsandwiched between the inventive polyurethane composition foamed panelscan be useful to reduce sound transmission in environments werestructural features, such as walls, may be temporary or semi-permanent.

Such inventive SIP material can also find utility in locations wheredecorative wall features may be desired. Such decorative wall featurescan be enhanced by the ability to paint the polyurethane coating and/orto create faux surface applications, such as a “stucco look,” woodgrain, textured surface, or the like. In one example, the inventive SIPscan be used to provide separation between areas in interior officeenvironments or the like. Still further, the lightweight, but solidlooking, structural insulating panels can have utility in generatingtheatrical scenes or movie sets.

The low cost, lightweight nature, and ease of assembly with the SIPs ofthe present invention can be used in the construction of emergencystorage buildings, emergency structures, “tiny houses,” or the like. TheSIPs of the present invention save significant amounts of labor becausethe individual SIP panels can be manufactured to match constructionplans for a job site such that a plurality of numbered panel componentscan be produced in a climate controlled factory to match the precisedimensions to match the construction plans. This means that when theinventive SIPs are erected at the job site, the individual panelcomponents match the construction plans for the project with straightwall sections, corners, and all window and door openings in place. Theindividual SIPs can be configured in the factory with already installedwindows/doors or window/door openings for installation of windowson-site, electrical and plumbing componentry, and the like. Instructionscan be provided to facilitate construction. All or substantially allcomponents are ready to install with substantially little or no need forjobsite modification.

The SIPs can be configured to lock together using conventional methods,for example using metallic or plastic seaming welds. Fit can further beenhanced by “snap lock” fits between adjacent panels, much like would befound in laminate flooring or the like. Such a fit can be facilitated byincorporating at least an edge molding process during the panel curingoperation. The panels can be secured at the ceiling/roof and floorlevels using conventional methodologies. As would be known, structuresbuilt from conventional SIPs (e.g., foam sandwiched between OSB panels),while highly energy efficient in theory, often fail to live up to thedesired energy efficiency because of heat or cold egress through theseams. To avoid this problem, panelized structures are typically wrappedwith a polymeric material, with the seams thereof being carefully sealedwith appropriate tape to form an air barrier. This generates additionalwork and cost. Advantageously, the inventive SIPs can be grouted orchalked or taped at the seams thereof to form an airtight seal thatsubstantially avoids the need to use a housewrap material to form anairtight seal between erected panels in the finished structure.

Polyurethane Coated Fiber Cement Panels

Yet further, the polyurethane compositions can be used as coating forfiber cement siding. In this regard, the exterior or interior facingside of the siding or siding can be light-weighted by reducing thethickness of the fiber cement portion without reduction of thestructural strength of the material. As mentioned previously, theinventive polyurethane compositions exhibit a surprising amount ofstructural strength, as compared to other foamed polyurethanecompositions. The polyurethane coated fiber cement siding or panels areat least about 10% or about 20% or about 30% lighter in weight than afiber cement panel of the same thickness that is not coated.

Moreover, as would be recognized, fiber cement is prone to cracking.Care must then be taken when fastening the materials to a structure. Theinventive polyurethane coating provides a substrate for nails and screwsthat enhances retention thereof.

The polyurethane coated fiber cement siding and panels are alsoinsulative over conventional substrates.

Coated Concrete or Masonry

The inventive polyurethane compositions also show strong adhesion toconcrete or masonry surfaces. The adhered polyurethane coatings can belayers or foams, as discussed elsewhere herein. The coatings can providewaterproofing, decorative aromatic polyester polyether polyols (e.g.,stucco-like, wood grain), cushioning when foamed coatings are used, etc.

Laminate Flooring and Subfloors

Yet further, the inventive polyurethane compositions can also be used asa backing material for laminate flooring, such as to provide acured-in-place cushioning material and/or sound proofing material.Accordingly, when used as a backing for laminate flooring, the separatepolymeric floor underlayment material that is used between the top ofthe floor surface and the bottom of the laminate flooring could beeliminated. Alternatively, such coated laminate materials can exhibitlesser sound transmission and improved cushioning.

Polyurethane Coated Structural Steel Panels Having Insulative Properties

In further implementations, the polyurethane compositions of the presentinvention can be used to generate a steel faced SIP. Yet further, thepolyurethane composition can be foamed and sandwiched between two steelpanels to generate a SIP. Such SIPs are useful for building panelizedstructures, such as prefabricated buildings, as discussed elsewhereherein. Yet further, such panels can be useful for creating modular roomconfigurations, such as is often done in office environments.

While steel faced SIPs are known the art, generation of such SIPs usingthe in situ polyurethane composition of the herein can provide, in oneaspect, a more efficient manufacturing process. This is due to theelimination of a separate foam generation step and subsequent adhesionstep, as is currently required. In one example of this process, one orboth of an interior facing side on two steel panels can be coated withthe aromatic polyester polyether polyol and isocyanate components on aline. The coated sides can then be brought together shortly afterapplication. Each of the coated sides can then meld as part of thecuring process to generate a foamed interior sandwiched between twosealed panels. The polyurethane foam interior will be adhered to each ofthe interior sides of the steel panels as a result of the in situprocess discussed herein. As discussed previously, the unique andsurprising strength of the bond between the cured-in-place inventivepolyurethane compositions means that a separate adhesive layer is notneeded to ensure adhesion of the foam layer to the steel panel(s).

Polyurethane Foam Insulation Materials

The present invention provides foamed materials that can be used asinsulative panels for construction applications. In one implementation,the foamed materials can be fabricated into panels that exhibit at leastsome R-value that compares favorably with other types of insulationmaterial, such as glass-wool or XPS. In this regard, a 2 pcf foam madefrom the materials of the present invention will exhibit an R-value ofat least about 2 or about 3 at a thickness of about 1 inch or at leastabout 2 or about 3 at a thickness of about ½ inch. Additionally, incomparison to the fire tendency of XPS, insulation panels made from theinventive polyurethanes exhibit a greatly improved fire resistance, atleast because they are not derived from petrochemical materials as isXPS. Yet further, the recycled and sustainable content of panels madefrom the present invention can provide further benefits over insulationpanels prepared from XPS.

Polyurethane Foam Structural Materials

In significant further aspects, the present invention comprises rigidpolyurethane foam materials suitable for providing structural support ina construction setting or in other applications where structural foammay be indicated. In this regard, the structural polyurethane foammaterials can be “load-bearing,” as such term would be known to one ofordinary skill in the art. In other aspects, the structural foammaterials of the present invention can be used to generate lightweightcladding material, as such term is defined elsewhere herein.

Polyurethane foams generated from the inventive materials are useful incomposite constructions and fabrications to generate structural foammaterials useful in construction and other applications. The inventivefoams can comprise integral-skin foams, or self-skinning foams, whichcouple a high-density skin and a low-density core.

The structural foam materials derived from the inventive polyurethanecompositions of the present invention can be configured into a widevariety of sizes, thicknesses, and densities and, as such, caneffectively operate as a substitute for conventional building materials.In this regard, the structural foam materials of the present inventioncomprise flexural strength, light-weight, inherent mold resistance,substantial thermal resistivity, water-repellant, non-corrosiveattributes as well. The resultant material is very resilient, resistsdenting and has superior nail and screw retention (equal to or greaterthan certain woods) to that of other materials. The structuralload-bearing urethane will never rust, pit, peel, corrode or flake away.The resultant material is very ecofriendly and can be verifiably“green.”

Due to the strength and the light-weight characteristics of thematerial, there is less possibility of damage during shipment, storageon the jobsite and during installation. That is, the structural foammaterials of the present invention are substantially or completely waterresistant, which can not only reduce shipping and storage costs, butalso deterioration due to water damage.

The structural material can be cut and sawn just like wood. Notably, theinventive polyurethane materials can have a lower propensity to generateharmful dust when sawed, thus making these materials an alternative toconventional fiber cement materials. The structural foam materialscomprise impact resistance and, therefore, can be hammered, screwed andnailed much like wood. The structural foam materials are naturallyresistant to insects and therefore require minimal maintenance over thelife of the product.

In one aspect, the structural foam materials can be made in panel orsheet form using a laminator. As would be recognized, such methods allowpolyurethane sheets or panels to be manufactured continuously orsubstantially continuously. The aromatic polyester polyether polyols arecombined with the isocyanate components, blowing agent, and anyadditives, including any filler materials, via one or more mixing headsand the mixture laid down on a belt system. Dynamic mixing methodologiesare suitable for use herein. The panels can then be cut into smallerpanels of a desired length before or after curing.

In some aspects, the structural foam materials of the present inventioncan be formed in either an open cast mold process or a closed-moldprocess. In the open cast mold process, the aromatic polyester polyetherpolyol, isocyanate, blowing agent, and any additives are mixed andpoured into the open mold and allowed to cure, with the polyurethanereactant material present top/open part of the mold being kept levelduring the curing process. In the closed cast mold process, the aromaticpolyester polyether polyol, isocyanate, blowing agent and any additivesare mixed and poured into a mold part. The mold is then closed and themixture is allowed to expand and cure. The mold parts can incorporatepatterning to impart surface décor on the resulting structural foammaterials, such as a faux wood grain or stone-look pattern. The moldsused herein can be fabricated from a variety of materials such as HDPE,ultra-high molecular weight PE, polyethylene or silicone.

Yet further, pultrusion processes can be used. As would be recognized, apolyurethane pultrusion system typically includes a two-part meteringunit, an injection chamber, additional heat zones and cooling zones. Theentire system is “closed” which shields the polyurethane from exposureto air and moisture. Pultrusion allows the incorporation of carbonfiber, glass, aramid and basalt reinforcements in applications rangingfrom complex shapes and heavy wall structural shapes, to thin wallhollows, and all-roving profiles.

To provide the requisite structural characteristics in constructionapplications, a minimum density of at least about 15, or about 20, orabout 25, or about 30, or about 35, or about 40, or about 45 or greaterpcf is provided by the structural polyurethane foam materials of thepresent invention. Lower densities can be appropriate for insulationapplications.

A notable aspect of the structural foam materials of the presentinvention is the adhesive characteristics exhibited by the polyurethanecomposition of the present invention. Such adhesive characteristicscould dictate that the inventive polyurethane composition not be used infor applications in which the adhesion would cause problems in amanufacturing environment. Indeed, a highly adhesive polyurethanematerial would not be selected for use to generate molded, pultruded orcast poured construction products, at least because, upon curing, thepolyurethane composition would stick to the mold, belt, etc. Theinventors herein have surprisingly determined that the polyurethanecomposition of the present invention, while exhibiting remarkableadhesive properties, can nonetheless show utility as structural buildingmaterials for use in construction applications.

In significant aspects, the polyurethane structural foam materials ofthe present invention will comprise at least some mold release agent ona surface thereof upon removal from the mold, belt etc. Moreover, atleast some of the mold release agent will remain on the surface of thecured material in use.

Structural Foam Construction Cladding

When configured into sizes consistent with conventional buildingmaterials, the structural foam materials of the present inventionprovide significant benefits over other forms of cladding (e.g., wood,fiber cement, aluminum, vinyl, etc.) and, therefore, can comprise asubstitute in residential and commercial construction applications. Thestructural foam materials of the present invention are suitable for usein creating lightweight facades, wall systems, soffits, fascia elements,window elements, and trim elements. Yet further, the structural foammaterials as cladding can be implemented as a stand-alone claddingsystem or a feature of rain barriers, rain screens, composite panels,fiber-cement board, glass-fiber reinforced concrete as well as metals orother materials. The inventive material can also be utilized as part ofan air barrier system or moisture barrier protections, and arethemselves moisture resilient and can impart moisture resiliency to thestructure in which they are incorporated.

Architects and material specifiers generally select cladding systemsbased upon aesthetics, performance needs, and suitability to theirapplication. Continuous insulation is a major component in the selectionprocess. The type of construction, climate zone and the building'sintended use are part of the determining factors. Whether the continuousinsulation component is interior to the structure or to be an outsidelayer of the structural framing is also a relevant decision. Much of thecontinuous insulation requires specialty clips, screws and sealingwashers to install continuous insulation materials. Some fasteners aredesigned to support the insulation only.

When configured in the form of cladding material, the polyurethanematerials of the present invention are structural in nature, while alsoexhibiting insulative value and the strength necessary to accommodatemost standard fastener systems. As shown in the examples, hereinafter,Cobb Ring testing revealed that substantially no water penetrationoccurred through the fastener which indicates that the material is“self-healing” around the fastener itself.

For use as cladding, the structural foam materials can be supplied in awide variety of sizes. For siding material, the structural foammaterials can be provided in about 6, 8, 10, 12 foot lengths with aheight of from about 4, 6, 8, 12 or more. Thickness can be from about ¼,½, ⅝, ¾, or 1 inch or more. When provided in sheet form, the structuralfoam materials can be provided as specified for a particularapplication, such as in about 4 to about 8 or about 4 to about 10 footsheets, having thicknesses as previously stated.

The polyurethane compositions of the present invention can be used asinterior or exterior wall or flooring components. Panels can begenerated in a number of sizes, as would be appreciated. In non-limitingexamples, the panels can be about 2, 4, 6, 8, 10 or 12 feet in length orwidth. Thickness can be from about ½, ⅝ inch, inch, 1 inch, 1¼, 1½, 1¾or 2 or more inches in thickness. Any of these length or width orthickness values can be used.

In various aspects, the wall systems can be used in industrial settingswere durability is desirable, for garage doors, for sporting venues,seawalls, and the like. The load-bearing characteristics of thepolyurethane materials of the present invention means that wall,roofing, and flooring structures that will be subject to pressures frommaterials pressing thereon can benefit from use of the inventivepolyurethane materials. Moreover, the substantial water-impermeabilityof the inventive materials make them particularly suited for use in wetlocations. The impact resistance and resiliency also make the materialsuseful in location where objects may come into contact with the wallmaterials. In this regard, the structural foam material is resistant tohail damage when used as a roofing material.

Structural Foam Filling Material

The present invention can be used to generate foam materials that can beused to fill cracks, voids, porosities, holes, or openings etc. inconcrete, wood, soil, rock, or the like. For example, when foamed, thematerials herein can be used to fill cracks in concrete structures(driveways, roadways, cement blocks) while at the same time restoring atleast some of the structural strength lost upon appearance of the cracketc. Yet further, the foamed materials can be used provide both fill andto restore structural support for ground-based locations havingsinkholes, cracks, etc.

Structural Foam Building Blocks

In some aspects, the polyurethane foam materials of the presentinvention can be configured in block form in conventional size (i.e.,cement blocks, masonry materials, etc.) or in custom size (i.e., cut tospecification). When in this configuration, the blocks comprise a highcompressive strength for support, for example to support roof-columnloads. The inventive blocks also resist distortion under load over time.In this regard, the inventive blocks can have a compressive strength ofat least about 350, 500, 1,000, 1,500 or greater as measured by D-1621The inventive blocks have a density of about 20 pcf or greater, or 25pcf or greater, or 30 pcf or greater or 35 pcf or greater.

Shaped Structural Polyurethane Foam Materials

The inventive polyurethane materials can be used to generate componentsthat provide shaped structure in as intended application, that is,provide load-bearing characteristics, in specifically required shapes.In this regard, the compositions of the present invention can be used aslumber substitutes or in tandem with a variety of applications, forexample, as I-beams, H-beams, I-joists, or the like. Yet further, theinventive compositions can be fabricated into traffic controlstructures, such as guard rails or traffic barriers. Yet further, round,fluted or hexagonal shapes can be generated for used as power poles,columns, pipes, etc. Materials made for such applications can begenerated from pultrusion processes, for example. Using pultrusion, forexample, much larger structures can be generated than can be generatedfrom injection molding techniques. In this regard, the shaped structuralpolyurethane materials are not prepared from injection moldingtechniques.

Polyurethane Spray Foam Insulation and Sealant Foams

Environmental control within a building envelope depends on stronginteraction between heat, air, and moisture transport collectively. Thepolyurethanes of the present invention can be used to provide a sprayedon insulation. In this regard, the blowing agent and spraying conditionscan be adjusted to provide a high density foam (for example, about 24 toabout 32 kg/m³ [1.5 to 2 pcf]) or a low density foam (for example lessthan about 8 Kg/m³ [0.5 pcf]). The polyurethane of the present inventioncan also be used to provide a sealant foam.

Other Applications

The polyurethanes of the present invention can also be used asstructurally strong, as well as fire resistant, linings for pipes,pipelines etc. For example, a damaged pipe can be sprayed to fill andcover any parts that are cracked, frayed, etc. Yet further, a pipe canbe coated with prior to use to reduce the possibility that the pipe willbecome damaged in use.

The polyurethanes of the present invention can also be used foraerospace applications, for example. In this regard, the materials havebeen shown to wet out carbon materials (e.g., fibers) that are commonlyused in generating components for aerospace products.

The materials of the present invention can also be used in insulativeapplications, such as for lining of trailers, railcars, etc. to allowtemperatures to be maintained within a desired range. For example, fortransportation of products through hot or cold areas, a temperature canbe maintained at above freezing, or above about 40° C. and below about110° C., or below about 105° C., even though the exterior temperature isbelow or above a temperature at which damage may result to the productbeing transported therein. Such insulative properties are accompanied bythe structurally strong properties of the inventive polyurethanes, thusproviding additional benefits.

The materials of the present invention can be used to create structuralcomponents for vehicles (e.g., automobiles, busses, trucks, aircraftetc.) where structurally strong, but lightweight materials areindicated. For example, the materials can be used to generate seatingcomponents and panels for aircraft. Panels and parts for automobiles canalso be made from the inventive composition.

Yet further, the materials can be used to in sporting applications, suchas in the fabrication of surfboards, skateboards, helmets, snow andwater skis, portable dance floors, and the like.

The inventive polyurethane materials can also be used in medicalapplications such as, X-ray and diagnostic tables, in medical devices,prosthetic devices, casings for instrumentation, or the like.

Describing now in more detail the drawings, numerals are included tospecify unique aspects and like components of the drawings throughoutvarious views or intended applications. Utilization of each object ofthe present disclosure may be used in any wall or ceiling application asdeemed necessary.

FIG. 2a represents a composite panel 200 having a substrate panel 205 inwhich the substrate panel 205 is coated on an interior side 210 (notshown) with, and therefore is adhered to, a cured-in-place polyurethaneadhesive foam layer 215 at interior side 220. Substrate panel 205 cancomprise a variety of materials, including gypsum drywall, wood (e.g.,plywood, OSB, etc.), cement, expanded or extruded polystyrene,polyurethane, metal, fiberglass, among other things,

FIG. 2b represents a side view orientation of composite panel 200showing the layering of substrate 205 and polyurethane foam layer 215with adhered interface 225, which can be at one or more locations, orcan be as a continuous layer. The polyurethane layer, can be from about25 to about 100% of the total thickness of the building panel. In thisnon-limiting example, the composite building panel has a total thicknessof about “and the polyurethane layer thickness of about 1 to 1½” more orless.

FIGS. 3a and 3b illustrate a composite panel 300 having a substrate 305coated with an unfoamed polyurethane coating 310 adhered to thesubstrate 305 at an interface 315. Composite panel 300 has substrateouter surface 320 and coating outer surface 325. Substrate panel 305 cancomprise a variety of materials, including gypsum drywall, wood (e.g.,plywood, OSB, etc.), cement, expanded or extruded polystyrene,polyurethane, metal, fiberglass, among other things

FIGS. 4a and 4b illustrate a composite sandwich panel 400 having a firstbuilding panel substrate 405 and a second building panel substrate 410having a foamed polyurethane adhesive layer 415 adhered at firstbuilding substrate inner surface 420 (not shown) and second buildingsubstrate inner surface 425. Substrate panel 405 can comprise a varietyof materials, including gypsum drywall, wood (e.g., plywood, OSB, etc.),cement, expanded or extruded polystyrene, polyurethane, metal,fiberglass, among other things.

FIG. 5 illustrates structural foam materials 500 in the form of a foamedpanel having outer surfaces 505 and 510 (not shown), as well as foamedinterior portion 515.

FIG. 6 illustrates foamed panel structure 600 having outer surface 605.While FIG. 6 illustrates structure 600 configured as a siding material,including illustration of embossed surface 605 providing a simulated or“faux” wood-grain finish.

FIG. 7 illustrates generic residential structure 700 having room 705,bathroom 710, and attic 715. The composite building substrates of thepresent invention can be used in a variety of locations in residentialstructure 700. For example, a coated drywall 720 can be used in room 705or bathroom 710. Structural floor panel 725 can be used as asubfloor/joist. Structural wall panel 730 can be used below coateddrywall 720. Composite underlayment panel 735 is also contemplated.Composite panel 740 is thicker than 730 to indicate a thicker insulationmaterial 745, as is often desirable in a roofing location as shown.Composite roofing panel 750, which is comprised of polyurethane coatedOSB, for example, is further shown having shingles 755 affixed thereto.Siding 765 can also be used in residential structure 700, as well as insoffit 770 and fascia 775. As would be recognized, the illustratedcomposite panels and uses thereof can be used alone or in combinationand the presented examples are intended to be non-limiting.

FIG. 8 illustrates a typical section for a commercial roof and wallcladding system 800. The structural foam materials and/or compositematerials can be incorporated in one or more of the describedcomponents. In this regard wall facing or finish 805 can be externallyfacing structural foam materials on outer wall 810, for example. A layerof the structural foam materials can be used as air barrier 815.Structural insulation panel 820 can be incorporated on an interiorportion of outer wall 810. In roof area 825, coping 830, as well asvarious configurations of the inventive building materials can be usedin the form as light weight roof deck 835, air barrier 840, insulation845, water control cladding 850, structural sheathing 855, rigidsheathing insulation 860, and air barrier roof sheathing 865. On aninterior side 870, the inventive materials can be used as structuralbeam 875. On interior wall 880, the inventive materials can beincorporated as a structural framework 885.

FIG. 9 illustrates an encapsulated material 900, in which a substrate,for example, a component 910 that is fully coated with the inventivepolyurethane coating 905. Component 910 can be any material that isdesirable for coating with inventive polyurethane coating 905, forexample, wood, concrete, metal, fiberglass, among others.

FIG. 10 shows I-joist 1000 having lateral section 1005 affixed betweenends 1010 a and 1010 b. Lateral section 1005 is shown with inventivepolyurethane foam 1015 coated thereto (and the opposite side thereof-notshown). I-joist 1000 can be used in building applications where fireresistant characteristics are desired.

Now having described the aspects of the present disclosure, in general,the following Examples describe some additional aspects of the presentdisclosure. While aspects of the present disclosure are described inconnection with the following examples and the corresponding text andfigures, there is no intent to limit aspects of the present disclosureto this description. On the contrary, the intent is to cover allalternatives, modifications, and equivalents included within the spiritand scope of the present disclosure.

EXAMPLES

The following examples are put forth so as to provide those of ordinaryskill in the art with a complete disclosure and description of how thecompounds, compositions, articles, devices and/or methods claimed hereinare made and evaluated, and are intended to be purely exemplary of thedisclosure and are not intended to limit the scope of what the inventorsregard as their disclosure. Efforts have been made to ensure accuracywith respect to numbers (e.g., amounts, temperature, etc.), but someerrors and deviations should be accounted for. Unless indicatedotherwise, parts are parts by weight, temperature is in ° C. or is atambient temperature, and pressure is at or near atmospheric.

Example 1. Preparation of Aromatic Polyester Polyether Polyols

Glycerin materials modified via ethoxylation were obtained from EthoxCompany (Greenville, S.C.) as prototype samples. The PET had an I.V. of0.83 (DAK 7000, Dak Americas, Charlotte, N.C.). The following materialsin the indicated amounts were used in the procedure that follows hereinbelow: ethoxylated triol-glycerin or trimethylolpropane with 5 molesethoxylation, 70.0 wt %; polyethylene terephthalate, 29.99 wt %; Fascat4201, 0.01 wt %. Briefly, the procedure was carried out as follows:

(Step 1) All ingredients were added with good agitation to a clean, dry,hot reactor capable of heating to 250° C. An overhead condenser may benecessary for a slight removal of water and some ethylene glycol, butsuch removal can be optional.

(Step 2) Began a nitrogen sparge to remove oxygen that may be dissolvedin the triol and start heating. The nitrogen sparge was controlled toensure that ethylene glycol was not rapidly removed from the mixture, asit was found if the sparge was too strong the viscosity of the mixturewould increase rapidly, resulting in a difficult to manage mixture. ThePET pellets contained some moisture that came off above 150° C. When thetemperature reached 170° C., a gentle nitrogen purge blanket wasapplied.

(Step 3) Continued heating to 240-245° C. Note: If heating cycle wasslow then the reaction could go to completion before 240° C. and so canbe sampled prior to 240° C. For this example conducted on a bench-scalereactor process, the heating was generated over about 2 hours. For anindustrial scale process, the time would be varied accordingly.

(Step 4) Began sampling for completeness of reaction. Once the hotsample was clear (e.g., no visible PET pellets), a Clear Pill Test wasconducted. Sampling was taken and for “Clear Pill” every 10 minutes.(Note that the appearance of a Clear Pill result was seen to vary fromreaction to reaction, depending, for example on the type and degree ofethoxylation for the triol, and the amount of PET used. The simplicityof the Clear Pill test allows such variability to be readily managed inuse, however.) Once a 10-minute Clear Pill was established, viscositywas checked. Depending on the reaction mixture ingredients, theviscosity at Clear Pill for the glycerin generated polyol was from about2.7 about 3.2 Poise using a Brookfield Cone and Plate with a #4 spindle,60° C., 100 rpm. (Note: for some samples, the viscosity evaluation wasrun at 70° C. This would be evident at the start for very viscousmaterials, for example, such as was seen with 2 moles ethoxylatedglycerin and 50% PET.)

(Step 5) The heating was continued at about constant temperature of 240°C. for 10 to 30 minutes to ensure completeness of transesterificationprocess and then heat was turned off. Checked viscosity when Clear PillTest completed every 15 minutes in this post-Clear Pill step. Note thatthis step, could be omitted in some implementations, however, as long asa Brookfield Cone and Plate Viscosity of 5 Poise or less (Spindle #4,60° C., 100 rpm) is generated. For PET transesterified with ethoxylatedglycerin, the target Brookfield Cone and Plate Viscosity after thesecond heating step was specified to be about 3.2 to about 3.7 Poise(Spindle #4, 60° C., 100 rpm) and from about 4.0 to about 5.0 Poise(Brookfield, spindle #4, 60° C., 100 rpm) was specified for an inventivepolyol generated from ethoxylated TMP. If viscosity was withinspecification the sample was cooled and prepared for storage by placingin an appropriate container. (Note: Viscosity increased quickly whencooled below 60° C., but will decrease upon application of heat foruse.)

Example 2. Testing Procedures for Reaction Mixture

Clear Pill Test: Several drops of product were placed on a clean drysurface. A cloudy appearance after 10 minutes indicated that the PET hadnot been suitably transesterified to generate the aromatic polyesterpolyether polyols of the present invention. Once clear for 10 minutesthe sample passed the Clear Pill Test. The Clear Pill Test was not anindication that the reaction is complete, rather that the catalyst isworking correctly. Completion of the reaction would typically take 10 to30 minutes longer at 240-245° C., as described in Example 1.

A Brookfield Cone and Plate viscometer was used because of speed oftesting, but other viscometers can be used. A #4 spindle at 100 rpm and60° C. was used for the Brookfield Cone and Plate method.

Hydroxyl Number of the ethoxylated triol was determined according tostandard test methodology, namely ASTM 4274-16, Test A.

Example 3. Effect of Varying Moles of Ethoxylation on Polyol Properties

The procedure to make these polyols was in accordance with the methoddisclosed above. The characteristics of the generated polyols were asset out below in Table 1.

TABLE 1 CHARACTERISTICS OF ETHOXYLATED GLYCERIN. Brookfield Cone Molesof Calculated and Plate viscosity cps ethoxylation M.W. of ethoxylatedglycerin on glycerin Hydroxyl # (g/mol.) (spindle #4, 60° C., 100 rpm) 11232 54.8 2 917 184 40.3 3 726 232 33.7 4 613 275 27.1 5 519 324 25.1 6461 365 23.1 7 419 402 23.1 9 345 488 24.4

Example 4. Glycerin-Derived Aromatic Polyester Polyether PolyolProperties

Samples were prepared using the procedure above, where each of thearomatic polyester polyether polyol preparations was conducted with 30%PET and 70% of the modified glycerin having the specified moles ofethoxylation. The samples were made into 25 g pucks to examine physicalproperties. 30% PET/70% ethoxylated glycerin-derived polyols from theprevious example were reacted with isocyanate at a 50:50 ratio. Thearomatic polyester polyether polyols and isocyanate were mixed and DBTLcatalyst was delivered during mixing with a pipette in one drop andallowed to cure in aluminum dishes for 24 hours. In the table below,“NT” indicates that the composition was not tested for the indicatedparameter. Data for Example 4 are provided in Table 2 below.

TABLE 2 PHYSICAL PROPERTIES OF INVENTIVE POLYURETHANES. Brookfield Coneand Plate PET/ethoxylated glycerin viscosity cps of 30% Initial 24 hourMoles of transesterification product weight weight 24 hour ethoxylation(spindle #4, of puck of puck Shore D on glycerin 60° C., 100 rpm) (g)(g) Hardness 1 220 NT NT NT 2 257 NT NT NT 3 265 NT NT NT 4 285 21.3521.36 80 5 283 21.36 21.37 77 6 327 20.95 20.97 82 7 361 20.35 20.36 819 413 21.65 21.66 76

Example 5. Comparison of Aromatic Polyester Polyether Polyols HavingSame Degree of Hydroxylation at Standard Isocyanate Composition

An examination of the effect glycerin ethoxylation on polyurethaneproperties at the same effective isocyanate level (in relation tohydroxyl number of the ethoxylated glycerin) was conducted. In thisregard, a 25 g amounts of 50:50 polyol:isocyanate mixtures (30% PET/70%ethoxylated glycerin) were mixed with 1 drop DBTL catalyst, where theglycerin had the indicated moles of ethoxylation. 5 moles ofethoxylation on glycerin was used as a baseline to vary the amount ofhydroxyl functionality among the samples by varying the amounts. Thereactions were conducted on aluminum plates from which the reactedmaterials could be removed as pucks for testing. Data for Example 5 areprovided in Table 3 below.

TABLE 3 PROPERTIES AT SIMILAR HYDROXYL VALUE. Initial 24 hour Moles ofRatio of weight of 24 hour weight Shore (D) ethoxylation* isocyanate**pucks (g) of pucks (g) Hardness 4 1.18 21.25 21.26 80 6 0.842 21.5321.54 81 7 0.806 20.44 20.44 79 9 0.664 22.14 22.15 74 *Moles ofethoxylation per mole glycerin that was used in preparation of aromaticpolyester polyether polyol. **Ratio of isocyanate to aromatic polyesterpolyether polyols.

Example 6. Moisture Regain Study

50:50 amounts of polyol:isocyanate (30% PET/70% ethoxylatedglycerin-derived polyols) were mixed with 1 drop DBTL catalyst, wherethe glycerin had the indicated moles of ethoxylation. The 25 g puckswere submerged in tap water for the indicated time at room temperature.As shown in the Table 4 below, moisture uptake was minimal for allsamples.

TABLE 4 MOISTURE REGAIN. Moisture % Difference Moles 24 48 72 96 120 148EO* hours hours hours hours hours hours 2 0.22 0.31 0.4 0.49 0.6 0.64 30.09 0.18 0.22 0.27 0.34 0.36 4 0.07 0.13 0.2 0.22 0.25 0.26 5 0.11 0.20.27 0.31 0.39 0.4 6 0.09 0.2 0.27 0.29 0.36 0.4 7 0.09 0.2 0.22 0.290.31 0.35 8 0.11 0.24 0.28 0.28 0.54 0.58 *Moles ethoxylation per moleglycerin

Example 7. Weight Change After 24 Hour Cure

Using the same procedure from the previous example of 50:50 ratios (30%PET/70% ethoxylated glycerin:isocyanate) fabricated into 25 g pucks wereevaluated for weight change after a 24 hour cure. Samples were kept atroom temperature and 50% humidity. The data are provided below in Table5. The data therein show that there is minimal weight change on curingfor 24 hours.

TABLE 5 WEIGHT CHANGE ON 24 HOUR CURE. Moles EO* % change in 24 hours 20.068 3 0.023 4 0.023 5 0.022 6 0.044 7 0.023 9 0.090 *Molesethoxylation per mole glycerin

Example 8. Flame Retardancy Data for Polyurethane Panel Made with PolyolDerived from Glycerin with 5 Moles Ethoxylation

A burn test was conducted to measure the heat transfer in degreesFahrenheit through a 1 inch foamed board made from the procedure inExample 1 at 30% PET/glycerin polyol component having 5 moles ofethoxylation with isocyanate (50:50 ratio) to which 2% TCPP was added.Density of the panel was approximately 24 pcf. The procedure was asfollows: (1) mount up the test specimen three inches from aBurns-O-Matic® torch tip, where the torch was also mounted; (2) activatethe torch; and (3) using an infrared thermometer, the temperature wasmeasured directly on the opposite side of the board specimen at eachminute for up to minutes. Data from this study are provided below inTable 6. The data show that the disclosed polyurethane compositions haveexcellent thermal behavior, especially when a flame retardant materialis incorporated therein. Accordingly, the materials are highly suitablefor use in construction applications.

TABLE 6 FLAME RETARDANCY DATA FOR FOAMED POLYURETHANE PANEL MADE WITHGLYCERIN HAVING 5 MOLES OF ETHOXYLATION AND 2% TPPP. Time (Minutes)Temperature (° F.) 0 73.1 1 74.1 2 75 3 75.2 4 75.6 5 76.2 6 77.7 7 81.18 84 9 88.8 10 93.3 11 96.4 12 103.8 13 107.3 14 111.7 15 116.2 16 120.717 129 18 146.3 19 147.5 20 155.1 21 166.6 22 172.7 23 179 24 181.2 25185.8 26 185.8 27 191.1 28 196.7 29 201.5

Example 9. R-Values for Foams at Different Densities

Foams were prepared with blowing agent at different densities as shownin the below Table and tested in for thermal properties. Expancel,product number 031 DU 40, was used as the blowing agent in the amountneeded to generate the indicated foam density. The aromatic polyesterpolyol was used was prepared from 70% ethoxylated glycerin (5 moles ofethoxylation) and 30% PET reacted at 50:50 ratio with isocyanate. Theprocess used was in accordance with the method of Example 1 above inaccordance with ASTM D5334-15 Standard Test Method for Determination ofThermal Conductivity of Soil and Soft Rock by Thermal Needle ProbeProcedure. The test instrument used was a KD2 Pro thermal analyzer witha KS-1 needle probe specific to insulation materials.

As shown by the Table 7, and accompanying FIG. 11, there is a fairlylinear relationship between foam density and R-value for thepolyurethane composition tested.

TABLE 7 THERMAL PROPERTIES OF AROMATIC POLYESTER POLYETHER POLYURETHANESAT VARIOUS DENSITIES.           Density (pcf) $\quad\begin{matrix}\begin{matrix}{Thermal} \\{Conductivity} \\\lbrack K\rbrack\end{matrix} \\\frac{W}{m*K}\end{matrix}$ $\quad\begin{matrix}\begin{matrix}{Thermal} \\{Resistivity} \\\lbrack p\rbrack\end{matrix} \\\frac{{cm}*{^\circ}\mspace{14mu} {C.}}{W}\end{matrix}$   $\quad\begin{matrix}\begin{matrix}{R\text{-}{value}} \\{{per}\mspace{14mu} {Inch}}\end{matrix} \\\frac{{ft}^{2}*{hr}*{^\circ}\mspace{14mu} {F.}}{{BTU}*{{in}.}}\end{matrix}$  2.0 0.037 2,710 3.91  3.0 0.038 2,600 3.75  5.2 0.0412,458 3.55  7.1 0.043 2,339 3.38 10.0 0.050 1,990 2.87 16.0 0.066 1,5142.19 24.0 0.117   850 1.23

Example 10. Impact Resistance of Ethoxylated Glycerin Polyurethane Pucks

25 g pucks were prepared from 50:50 polyol:isocyanate (30% PET/70%ethoxylated glycerin with varying moles of ethoxylation) and impactresistance tests were performed as shown below, where “Sample ID”conforms to the moles of ethoxylation of glycerin. As shown in Table 8below, 5 and 9 moles of ethoxylation shows excellent impact resistance.The tester noted that 9 moles of ethoxylation showed some indentation ofthe surface, thus possibly indicating that the surface was less hard.

TABLE 8 IMPACT RESISTANCE. Repetitive Impact Force at Drop Test 10Sample Failure or Max Failure lbs - 18 in. ID (in-lbs) Type HeightFailure Type 5 160 (max) No Failure 500 Blows No Failure - SignificantlyLess Indentation than #9 9 160 (max) No Failure 500 Blows No Failure 7160 (max) No Failure 350 Blows Cracked 4 160 (max) No Failure 250 BlowsCracked 3 140 Cracked 6 100 Cracked 2  40 Cracked

Example 11. Tests Conducted for Polyurethane Panels

A. ASTM D1621-16—Compressive Properties

Five 2 inch cubes specimens of inventive polyurethane panels formed weretested in accordance with ASTM D1621. The samples were conditioned to73±3.5° F. and 50±2% relative humidity for 24 hrs prior to testing. Therate of testing was 0.20 in/min. of crosshead displacement. The testmachine used for compressive testing was a Satec-Model 5590-HVLclosed-loop, dynamic servo-hydraulic, testing machine conforming to therequirements of ASTM E4-16 Standard Practices for Force Verification ofTesting Machines.

B. ASTM D695-10—Compressive Properties

Compressive properties were determined in accordance with ASTM D695using five 1.00″×2.00″ cylinders of inventive polyurethane panels. Thesamples were conditioned to 73±3.5° F. and 50±2% relative humidity for24 hrs prior to testing. The rate of testing was 0.05 in./min ofcrosshead displacement.

C. ASTM D570-10—Water Absorption

Water absorption was determined in accordance with ASTM D570. Three2.00″ diameter×0.25″ thick discs of inventive polyurethane panel wereused for testing. The samples were conditioned to 73±3.5° F. and 50±2%relative humidity for 24 hrs prior to testing. The disks were submergedin water for 24 hours. The initial and final weights were used tocalculate the percent absorption.

D. ASTM D732-10—Shear Strength of Plastics by Punch Tool

Shear strength properties were determined in accordance with ASTM D732.Three specimens of inventive polyurethane panel with approximatedimensions of 2″ diameter×0.25″ thickness were used for testing. A holein the center of each specimen was drilled with a lathe to a diameter of1″. The specimens were conditioned to 73±3.5° F. and 50±2% relativehumidity for 24 hrs prior to testing. The load was applied to thespecimens using a 0.999″ diameter punch at a rate of 0.05 in/min. ofcrosshead displacement.

E. ASTM D790-10—Procedure A—Flexural Strength & Flexural Tangent Modulus

Flexural strength properties of inventive polyurethane panels weredetermined in accordance with ASTM D790. Five specimens with aromaticpolyester polyether polyols generated polyurethanes having approximatedimensions of 2.00×0.50×10.00 inches were used for testing. The loadrate used in testing was 0.21 in./min. of crosshead displacement whichequates to a strain rate of 0.01 in./in. The span length used in testingwas 8.00 inches.

F. ASTM D648-07—Heat Deflection

Heat deflection temperature was determined in accordance with ASTM D648.Two 0.50″ by 0.50″ by 5.00″ test specimens of inventive polyurethanepanel were used for testing. The specimens were tested in the edgewiseposition under a 264 psi stress in accordance with ASTM D648. The rateof temperature increase was 2° C. per minute.

G. ASTM E96-16—Water Method—WVTR

The inventive polyurethane panel specimens used for water vaportransmission testing were approximately 3.50 inches in diameter×0.25inches in thickness and were saw cut on both faces. Specimens weretested using the water method. The test cups were filled with 970 g ofdistilled water to within 0.75 inches of the specimen. Specimens weresealed to the test cups using a commercially available 2 part adhesiveand tested at a temperature of 73.0±2° F. and a relative humidity of50±2%.

Data obtained for representative disclosed polyurethanes using theforegoing test methods are given below in Tables 9-10. Data are givenfor representative disclosed TMP panels using the foregoing test methodsare given below in Tables 11-19.

TABLE 9 COMPARATIVE PROPERTY SUMMARY FOR POLYURETHANES GENERATED FROMGLYCERIN OR TMP HAVING 5 MOLES OF ETHOXYLATION. Average Test Result ASTMTest Property Glycerin* TMP** D570 Absorption - 24 hrs (%) 4.1 4.16D2482 Dry Density (pcf) 25.9 23.0 SSD Density (pcf) 26.4 23.6 ApparentDensity (pcf) 26.1 23.2 Absorption - 96 hrs (%) 2.1 3.0 D648 HeatDeflection Temperature - 264 psi (° F.) 152.0 137.6 D2240 Shore DHardness - Skinned Surface 62 50 Shore D Hardness - Open Faced Surface32 33 D1621 Compressive Yield Strength (psi) 520 680 CompressiveStrength (psi) 890 1,080 Compressive Modulus (psi) 28,170 36,900 D790Flexural Strength (psi) 2,030 1,550 Flexural Tangent Modulus (psi)59,200 44,200 D695 Compressive Yield Strength - 0.2% Offset (psi) 1,560680 Compressive Strength (psi) 2,100 1,070 Compressive Modulus (psi)57,500 35,800 C531 Coefficient of Thermal Expansion (in./in./° F.)2.18E−04 NT D732 Shear Yield Strength (psi) 240 285 Peak Shear Strength(psi) 350 345 D96 Slope (grains/hr) 0.00899 0.10957 Method B Water VaporTransmission Rate 0.571 6.062 (lbs/24 hr/1000 ft²) Permeance (US Perm)0.43 4.53 *Glycerin refers to a polyurethane foam having a density of 24pcf generated per the disclosed methods from glycerin (30% PET/70%ethoxylated triol) having 5 moles of ethoxylation reacted withdiisocyanate at 50:50 ratio and 0.1% DBTL catalyst, formed into a panel,and cured for 7 days before testing. **TMP refers to a polyurethane foamhaving a density of 24 pcf generated per the disclosed methods fromtrimethylolpropane (30% PET/70% ethoxylated triol) having 5 moles ofethoxylation, reacted with diisocyanate at 50:50 ratio and 0.1% DBTLcatalyst, formed into a panel, and cured for 7 days before testing.

TABLE 10 ASTM D695: Compressive Properties with TMP Panel. YieldCompressive Load, Yield 0.2% Peak Strength, Peak Diameter Height Areaoffset Load 0.2% offset Stress Compressive ID (in.) (in.) (in.²) (lbf.)(lbf.) (psi) (psi) Modulus (psi) 1 1.000 2.038 0.7854 1,298 1,782 1,6502,270 63,700 2 1.016 1.959 0.8099 1,376 1,784 1,700 2,200 60,800 3 1.0161.988 0.8099 1,355 1,823 1,670 2,250 59,000 4 1.056 1.717 0.8758 1,2601,706 1,440 1,950 51,400 5 1.017 2.011 0.8123 1,099 1,504 1,350 1,85052,500 Average 1,560 2,100 57,500

TABLE 11 ASTM D1621: Compressive Properties with TMP Panel. Load StrainStrain Load at Stress Stress at at at Peak 10% at Peak at CompressiveWidth Length Height Area Yield Peak Yield Load Strain Yield Stress 10%Modulus # (in.) (in.) (in.) (in²) (in./in.) (in./in.) (lbf.) (lbf.)(lbf.) (psi) (psi) Strain (psi) 1 2.031 1.998 2.027 4.057 0.0195 0.13011633.3 2972.3 2805.1 403 733 691 22,431 2 2.030 2.038 1.992 4.137 0.02160.1302 2034.6 3457.4 3280.8 492 836 793 24,986 3 2.024 2.002 2.028 4.0510.0204 0.1301 2481.1 3970.2 3817.9 613 980 943 34,456 4 2.050 2.0002.010 4.099 0.0212 0.1301 1994.7 3476.6 3312.9 487 848 808 25,753 52.095 2.045 2.094 4.283 0.0198 0.1303 2626.2 4554.5 4308.8 613 1063 100633,245 Avg 2.046 2.016 2.030 4.125 0.0205 0.1302 2154.0 3686.2 3505.1520 890 850 28,174

TABLE 12 ASTM D790: Flexural Properties with TMP Panel. Flexural SpanPeak Flexural Tangent Width Depth Length Load Strength Modulus ID (in.)(in.) (in.) (lbf.) (psi) (psi) 1 1.973 0.514 8.00 84.3 1,945 62,855 21.948 0.480 8.00 77.3 2,065 68,425 3 1.997 0.506 8.00 81.4 1,910 58,9984 1.974 0.509 8.00 81.0 1,900 65,725 5 2.004 0.506 8.00 98.8 2,31040,140 Average 2,030 59,200

TABLE 13 ASTM D1621: Heat Deflection under Load with TMP Panel. Avg.Total Load Width Avg. Depth Applied (g) Heat Deflection Specimen # (in.)(in.) 264 psi Temperature (° F.) 1 0.4947 0.4913 2383.0 151.5 2 0.49670.4867 2357.3 152.5 Average 152.0

TABLE 14 ASTM D570 Absorption with TMP Panel. Initial Weight DiameterThickness Weight After 24 hr Difference % Specimen # (in.) (in.) (g)Soak (g) (g) Absorption 1 2.0235 0.2745 6.2010 6.4600 0.2590 4.18 21.9965 0.2420 6.2410 6.4730 0.2320 3.72 3 2.0155 0.2650 6.4090 6.69300.2840 4.42 Average 4.11

TABLE 15 ASTM D2482 Absorption and Density with TMP Panel. 96 hr Weightof Oven Relative Density Weight of SSD Pycnometer & Dry Density RelativeApparent Oven Density Apparent Pycnometer Weight Specimen Weight OvenDensity Relative Dry SSD Density # (g) (g) (g) (g) Dry SSD Density (pcf)(pcf) (pcf) Absorption % 1 1957.8 54.20 1890.20 53.10 0.436 0.445 0.44027.15 27.71 27.40 2.1 2 1965.9 52.30 1891.40 51.31 0.405 0.412 0.40825.20 25.68 25.40 1.9 3 1954.5 57.70 1886.80 56.59 0.451 0.460 0.45528.10 28.65 28.35 2.0 4 1954.5 54.10 1886.70 53.22 0.437 0.444 0.44027.19 27.64 27.38 1.7 5 1970.7 48.80 1884.80 47.51 0.353 0.362 0.35621.96 22.56 22.18 2.7 Avg 2756.7 53.42 1887.98 52.35 0.416 0.425 0.42025.92 26.45 26.14 2.1

TABLE 16 ASTM D732 Shear Strength by Punch Tool with TMP Panel. YieldYield Load at Stress Peak Average Punch 0.2% Peak at 0.2% Shear ShearDiameter Thickness Area offset Load offset Stress Stress Specimen #(in.) (in.) (in.²) (lbf.) (lbf.) (lbf.) (psi) (psi) 1 1.00 0.2753 1.7298387 551 220 320 350 2 1.00 0.2677 1.6820 371 595 220 350 3 1.00 0.28201.7719 477 675 270 380

TABLE 17 ASTM C532 Coefficient of Thermal Expansion with TMP Panel.Length at Length at Lower Upper Specimen Temp (° C.) Temp (° C.) COTE(in./in./ COTE (in./ Temperature 23 100 ° C.) in./° F.) 1 10.055010.3595 3.93E−04 2.18E−04 2 10.0750 10.3710 3.82E−04 2.12E−04 3 10.056010.3655 4.00E−04 2.22E−04 Average 10.0620 10.3653 3.92E−04 2.18E−04

TABLE 18 ASTM E96 - Water Vapor Transmission: Specimen and TestConditions with TMP Panel. Product Name: Expanded Foam Specimen Type ¼″Thickness - Saw Cut on Both Faces Method Used Water Dish Diameter (in.)3.152 Dish Area (sq. ft.) 0.054 Test Temperature (° F.) 73.0 Rel.Humidity (%) 51.2 Saturation Vapor Pressure 0.81 (in. Hg)

TABLE 19 ASTM E96 - Water Vapor Transmission with TMP Panel. SpecimenSpecimen WVTR & Permeability 1 2 Specimen 3 Average Slope of the Line,0.00877 0.00987 0.00975 0.00899 grains/h ·grains/hour · ft² 0.16 0.180.18 0.17 ·lbs/24 hour ·1000 ft² 0.557 0.627 0.619 0.571 ·grams/hour ·m² 0.11 0.13 0.13 0.12 ·US perms 0.42 0.47 0.46 0.43 ·grams/Pa · s · m²2.38E−08 2.68E−08 2.65E−08 2.44E−08

Example 12: Determination of R-Value of TMP Panel

A TMP panel (30% PET/70% TMP with 5 moles ethoxylation reacted at 50:50with isocyanate/1% DBTL) having a thickness of 1 inch was cut into a 12inch by 12 inch square.

A calibrated hot box was used to generate the R value of the inventivepolyurethane material. Calibration was conducted using materials havingknown R-values from 2-10. Data points collected were inside/outsideambient temperature and the inside/outside surface temperature of thetest specimen. A model was fit to the data and is given in FIG. 8.

Once the temperatures reached a steady state, the averages of a 24 hourperiod of temperatures (see FIG. 9) were used for calculating theR-value of the PET panel. The averages for data point are:

Inside Ambient 108.65 F. Inside Face 102.18 F. Outside Face  77.18 F.Outside Ambient  73.50 F.Therefore, the calculated R-value of the inventive PET panel is:

R-value of PET panel=45.69−(3.562*25)+(0.07284*252)=2.169

Another way to calculate R-value is by using the formula:

U1(TA−T1)=U2(T1−T2); and

U2=(U1(TA−T1))/(T1−T2);

where: U=Thermal Transmittance; T1=Interior Face Temperature; T2=OutsideFace Temperature; and TA=Interior Ambient. Given that the R-value is thereciprocal of the U-value, the calculation for R-value would be:

R2=R1(T1−T2)/(TA−T1);

where R1=Reciprocal of Thermal Transmittance of air=0.68; R2=R-value ofPET panel; R2=(0.68(102.18−77.18))/(108.65−102.18)=17/6.47=2.63. Bothways for determining the R-value of the PET panel are not significantlydifferent.

The R value tests demonstrate that the inventive polyurethane panelthickness of 1 inch exhibits an R value of greater than 2 according tothe provided test methodologies, thereby providing at least someinsulative properties. This data indicates that a coating having thesame characteristics will provide at least some insulative properties.

Example 13: Nail Insertion and Removal Performance of TMP Panel

A panel made from a polyurethane derived from a TMP panel (30% PET/70%TMP with 5 moles ethoxylation reacted at 50:50 with isocyanate/1% DBTL)was tested for screw retention were prepared into two 12 inch by 12 inchby 1 inch panels. The panels were milled using a table saw to have atongue and groove shape along the perimeter of the panels.

The panels were then nailed to a wall structure (Force Field,Georgia-Pacific LLC) using finish nails (nailed at an angle through thetongue into the wall structure and face nailed with finish nails abovegroove). Both panels were placed together so that the correspondingtongue and grooves fit together leaving a small gap between the panels.The nail holes in the face of the panel were puttied with glazingcompound and the panels painted.

The inventive polyurethane panel nailed easily to the wall structure andheld well with finish nails. The small hole created by the finish nailmade the glazing of the nail holes easy. The panels painted well. Whenthe panels were removed, the nails came off with the panels. No nailswere left in the wall structure which indicates good nail holdingability for the inventive polyurethane material in panel form. It can beinferred that a coating of the polyurethane material would impartsimilar nail retention characteristics.

Example 14: Tape Adhesion Testing of TMP Panel

A TMP panel (30% PET/70% TMP with 5 moles ethoxylation reacted at 50:50with isocyanate/1% DBTL) was tested for tape adhesion by fastening tapeacross two sides of the panels, with the panels being arranged side byside so that there was a ¼″ gap between each panel. Two inch widemodified rubber tape was used to seal the gap between the panels and a 4inch Cobb Ring was attached over gap and tape to measure waterpenetration through the tape seams. The Cobb Ring was filled with oneinch of water (as measured on the interior of the ring). The water levelwas raised to 2 inches for another 24 hours with no signs of leaking.The water level was raised to 3 inches for a 24-hour period and still noleaking observed. No sign of leaking from the tape edges was observed,demonstrating that tape adhesion to the inventive polyurethane materialwas excellent. It can be inferred that a coating of the polyurethanematerial would impart similar tape adhesion characteristics.

Example 15 Water Seepage Properties of TMP Panel

Two 2 inch screws were screwed into a TMP panel (30% PET/70% TMP with 5moles ethoxylation reacted at 50:50 with isocyanate/1% DBTL). The screwswere driven into the panel until the head of each screw was flush withthe panel surface. The water level was raised to 2 inches for another 24hours with no signs of leaking. The water level was raised to 3 inchesfor a 24-hour period and still no leaking observed. The Cobb Ring wasfilled with one inch of water (as measured on the interior of the ring).The water level was raised to 2 inches for another 24 hours with nosigns of leaking. The water level was raised to 3 inches for a 24-hourperiod and with still no leaking observed. The absence of water leakagefrom inside the Cobb Ring indicates that water seepage did not occur asa result of disruption of the internal structure of the polyurethanematerial. This indicates that the screw retention and “grab” of thematerial to screws is excellent, and aromatic polyester polyetherpolyols to demonstrate that the inventive polyurethane material exhibitsresiliency upon insertion of screws, for example. The results indicatethat the inventive polyurethane material shows a propensity to sealaround fasteners, keeping liquid water from seeping through the materialreaching the wood structure where it can cause problems. Also, the lackof water leakage indicates that seepage into structural componentspositioned below the coating is unlikely. Such lack of seepage is abenefit in construction applications. It can be inferred that a coatingof the polyurethane material would impart similar characteristics.

Example 16: Nail and Screw Pull Test of TMP and Glycerin Panels

A 1 inch thick of each of a TMP and glycerin panel were prepared. (30%PET/70% glycerin or TMP each with 5 moles ethoxylation reacted at 50:50with isocyanate/1% DBTL). A fastener was inserted into the test boardwith a portion remaining exposed. Density of the panel was about 24 pcf.

The pull test was conducted as follows. The Com-Ten FG-1000 AnalogFastener Tester was placed over each test sample so that the entirety ofthe tester was positioned on the sample, and the screw in the sample wasattached to the power screw on the testing device. The torque bar wasturned clockwise until the top of the foot engaged slightly with thehead of the screw. The black pointer on the device was set to zero, andthe red pointer were set to zero prior to starting the test. Pressurewas applied to the screw by continuous turning of the torque bar handlein a clockwise motion to apply tensile pull on the fastener. Each fullturn of the handle moved the power screw 0.10 inches. Continuous forcewas applied by the screw until a maximum point was reached and the blackpointer dropped off. The resulting force was measured in pounds on thegauge. The red pointer on the gauge was read to provide the maximumyield or break point of the fastener.

A 1 inch wood screw (Everbilt) was inserted into the 1 inch thick panelwith about ⅜ inch remaining exposed. A pull test was performed. Theinventive polyurethane panel exhibited a required pull test result of360 pounds (glycerin) and 340 pounds (trimethylolpropane). Theseexamples demonstrate that the inventive polyurethane panels in panelform exhibit excellent screw retention.

Example 17: Screw Retention of OSB Panel Coated with PolyurethaneDerived from Ethoxylated TMP

A ½ inch piece of OSB (Norboard) was coated with 20 mils of apolyurethane coating was prepared using the aromatic polyester polyolderived from trimethylolpropane having 5 moles of ethoxylationtransesterified with PET at a 30% PET/70% triol ratio, where the polyolwas reacted at a 50:50 ratio with diisocyanate (1% DBTL). A #10 by 1inch flat head Phillips wood screw (Everbilt) was inserted into thecoated OSB board to a depth of inch. A control board of uncoated ½ inchOSB was also tested with the same screw parameters.

The pull test technique set out above was used to test the screwretention of each OSB. The measured force to remove the screw from thecoated OSB board was 480 pounds. The measured force to remove the screwfrom the uncoated OSB board was 310 pounds. The results show that theinventive polyurethane coating improves the screw retention of OSBboard, and has utility in roofing applications, as an example.

It will be apparent to those skilled in the art that variousmodifications and variations can be made in the present disclosurewithout departing from the scope or spirit of the disclosure. Otherimplementations of the disclosure will be apparent to those skilled inthe art from consideration of the specification and practice of thedisclosure disclosed herein. It is intended that the specification andexamples be considered as exemplary only, with a true scope and spiritof the disclosure being indicated by the following claims.

1-20. (canceled)
 21. An foamed aromatic polyester polyether polyolcomposition, wherein the aromatic polyester polyether polyol has astructure that is either: a. based on a glycerol backbone, the structurerepresented by a formula:

wherein each of R₁, R₂, and R₃ is independently selected from hydroxyland a structure represented by a formula:

provided that at least one of R₁, R₂, and R₃ is not hydroxyl; wherein mhas a value such that the aromatic polyester polyether polyol has aBrookfield Cone and Plate Viscosity of less than about 5 Poise carriedout using Spindle #4 at 100 rpm and 60° C.; and wherein each of n₁, n₂,and n₃ is an integer independently selected from 0, 1, 2, 3, 4, 5, 6, 7,8, and 9, provided that a sum of the values for n₁, n₂, and n₃ is 1 to9; or b. based on a trimethylolpropane backbone, the structurerepresented by a formula:

wherein each of R₁, R₂, and R₃ is independently selected from hydroxyland a structure represented by a formula:

provided that at least one of R₁, R₂, and R₃ is not hydroxyl; wherein mhas a value such that the aromatic polyester polyether polyol has aBrookfield Cone and Plate Viscosity of less than about 5 Poise carriedout using Spindle #4 at 100 rpm and 60° C.; and wherein each of n₁, n₂,and n₃ is an integer independently selected from 0, 1, 2, 3, 4, 5, 6, 7,8, and 9, provided that a sum of the values for n₁, n₂, and n₃ is 1 to9.